Supporting Information
|
|
- Simon Simpson
- 5 years ago
- Views:
Transcription
1 Supporting Information F Nucleophilic-Addition-Induced Allylic Alkylation Panpan Tian,,, Cheng-Qiang Wang,, Sai-Hu Cai,, Shengjin Song,, Lu Ye, Chao Feng, *, and Teck-Peng Loh *,, Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University Department of Chemistry, University of Science and Technology of China Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore iamcfeng@njtech.edu.cn teckpeng@ntu.edu.sg. Table of Contents Page No General Information S-2 Experimental Section S-2 Substrate Synthesis S-2 Condition Optimization S-5 Palladium-catalyzed NAAA reaction S-10 Characterization of structurally novel compounds S-11 Reference S-22 1 H 19 F and 13 C NMR Spectra of structurally novel S-23 compounds S1
2 General Information Pd(MeCN)4(BF4)2 was purchased from Chemical Service and used as received. All reactions were carried out under air without extra protection unless otherwise noted. Reactions were monitored through thin layer chromatography [Merck 60 F254 precoated silica gel plate (0.2 mm thickness)]. Subsequent to elution, spots were visualized using UV radiation (254 nm) on Spectroline Model ENF-24061/F 254 nm. Further visualization was possible using basic solution of potassium permanganate as stain. Flash chromatography was performed using Merck silica gel 60 with distilled solvents. HRMS spectra were recorded on a Waters Q-Tof Permier Spectrometer. 1 H NMR and 13 C NMR spectra were recorded using Bruker Avance 400 MHz spectrometers. Chemical shifts for 1 H NMR spectra are reported as δ in units of parts per million (ppm) downfield from SiMe4 (δ 0.0) and relative to the signal of SiMe4 (δ 0.00, singlet). Multiplicities were given as: s (singlet); d (doublet); t (triplet); q (quartet); dd (doublets of doublet); ddd (doublets of doublets of doublet); td (triplet of doublet); m (multiplets) and etc. Coupling constants are reported as a J value in Hz. Carbon nuclear magnetic resonance spectra ( 13 C NMR) are reported as δ in units of parts per million (ppm) downfield from SiMe4 (δ 0.0) and relative to the signal of chloroform-d (δ 77.00, triplet). Experimental section Substrates preparation gem-difluoroalkene examined: 1a-1g were synthetized following reported method. 1-2 Method I: (1h, 1i were synthetized using this method). S2
3 Synthetic procedure: Hexamethylphosus triamide (HMPT) (3.5 eq.) was added dropwise over 10 min to a solution of dibromodifluoromethane (1.9 eq.) in dry THF at -78 C. The reaction mixture was warmed to rt and a solution of aldehyde or kentone in THF was added over 10 min. After being stirred at rt for 5 h, the mixture was diluted with PE and quenched with water, the layers was separated, and the aqueous layer was extracted with PE. The combined organic phase was washed with brine, dried over Na2SO4, filtered and concentrated in vacuo and purified by chromatography on silica gel to afford the corresponding title compound. Method II: (1j-1o were synthetized using this method). Synthetic procedure: A 25 ml screw-top vial was charged with the corresponding ketones (0.600 mmol), Ph3P + CF2CO2 (429 mg, 1.2 mmol) and a stir bar, sealed, evacuated and backfilled with N2, DMF (2 ml) was added via syringe. The vial was placed in a 60 C heating block, and the reaction mixture was stirred for 8h, The combined organic phase was washed with water, extracted with Et2O, dried over Na2SO4, filtered and concentrated in vacuo and purified by chromatography on silica gel to afford the corresponding compound. Reaction scheme for 1l synthesis: Synthetic procedure: a) To a solution of 6-hydroxy-3,4-dihydronaphthalen- 1(2H)-one in pyridine at 0 C, Tf2O was added dropwise under an nitrogen atmosphere. After being stirred at rt for 18 h, the mixture was quenched with water and extracted with ether. The combined organic phase was washed with 1M HCl and brine, dried over Na2SO4, filtered and concentrated in vacuo and purified by chromatography on silica gel to afford the corresponding triflate. b) A mixture of triflate obtained above, Pd(OAc)2 (0.07 eq.), dppp (0.065 eq.), Et3N (3 eq.) in anhydrous DMF/MeOH (2:1, 0.2M) was stirred at 70 C and purged with CO for 5 min after which the mixture was stirred under 1 atm of CO overnight. The mixture was cooled to rt and poured into brine, extracted with ether. The volatile compounds were removed in vacuo and purified by chromatography on silica gel to afford methyl ester. (The ensuing procedure follows Method II). S3
4 Allyl tert-butyl carbonate examined: Reaction scheme for allylic alcohol synthesis: Synthetic procedure: Aldehyde (1 eq.) was dissolved in dry THF at 0 C. Vinylmagnesium bromide (1.2 eq. 1 M in THF) was added slowly into above solution and the mixture was stirred overnight. Then saturated NH4Cl was added and extracted with EA, dried over Na2SO4, filtered, evaporated and the residue was purified by chromatography on silica gel to afford the corresponding substitutive allylalcohol. Method I: (2a-2l were synthetized using this method). Synthetic procedure: n- BuLi(1.1 eq.) was added slowly to a solution of substitutive allylalcohol (1 eq.) in dry THF at 0 C. After stirring the resulting solution for 30 min, (Boc)2O (1.5 eq.) was added. After the full consumption of the substitutive allylalcohol the mixture was quenched with aqueous saturated NaHCO3, extracted with EA and washed with saturated brine. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo and purified by chromatography on silica gel to afford the corresponding title compound. Method II: (2m-2o were synthetized using this method). S4
5 Synthetic procedure: NaH(1.3 eq.) was added to a solution of substitutive allylalcohol (1 eq.) in dry THF at 0 C. After stirring the resulting solution for 15 min, (Boc)2O (1.5 eq.) was added. After the full consumption of the substitutive allylalcohol the mixture was quenched with aqueous saturated NaHCO3, extracted with EA and washed with saturated brine. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo and purified by chromatography on silica gel to afford the corresponding title compound. Method III: (2p-2s were synthetized using this method). Synthetic procedure: DMAP (0.2 eq.) and (Boc)2O (1.5 eq.) were added to a solution of substitutive allylalcohol (1 eq.) in DCM at rt. After the full consumption of the substitutive allylalcohol the mixture was quenched with aqueous saturated NaHCO3, extracted with EA and washed with saturated brine. The organic layer was dried over Na2SO4, filtered and concentrated in vacuo. The resulting crude solid was purified by chromatography on silica gel to afford the corresponding title compound. Reaction conditions optimization Table 1: Solvent screening Procedure: An oven-dried 10 ml Schlenk tube was charged with Pd(OAc)2 (5.0 mol%), X-phos (10 mol%), CuOAc (10 mol%), CsF (0.45 mmol) in sequence under the glovebox, followed by adding 1a (0.15 mmol) and 2a (0.3 mmol) and then S5
6 anhydrous solvent (1.0 ml) was added through syringe. After stirring at 80 o C for 10 h the mixture was washed with water and extracted with Et2O, the solvent was removed in vacuo. Purification of the residue by silica gel column chromatography afforded the desired product 3a. Table 2: Ligand screening S6
7 Table 3: Additive screening S7
8 Table 4: Fluoride screening S8
9 Table 5: Catalyst and temperature screening S9
10 Table 6: Control experiments General procedure for palladium-catalyzed NAAA reactions Procedure A: An oven-dried 10 ml Schlenk tube was charged with Pd(CH3CN)4(BF4)2 (5.0 mol%), X-phos (10 mol%), CuF2 (10 mol%), CsF (0.45 mmol) in sequence under the glovebox, followed by adding 1 (0.15 mmol) and 2 (0.3 mmol) and then anhydrous DMF(1.0 ml) was added through syringe. After stirring at 60 o C for 10 h the mixture was washed with water and extracted with Et2O, the solvent was removed in vacuo. Purification of the residue by silica gel column chromatography afforded the desired product 3. Procedure B: An oven-dried 10 ml Schlenk tube was charged with Pd(CH3CN)4(BF4)2 (5.0 mol%), Xantphos (10 mol%), CuF2 (10 mol%), CsF (0.45 mmol) in sequence under the glovebox, followed by adding 1 (0.15 mmol) and 2 (0.3mmol) and then anhydrous DMF(1.0 ml) was added through syringe. After stirring at 60 o C for 10 h the mixture was washed with water and extracted with Et2O, the solvent was removed in vacuo. Purification of the residue by silica gel column chromatography afforded the desired product 3. (For the gem-difluoroalkenes examined only the p-no2 derived one 1g would afford the bis-allylation products, because the nitro substituent was electron-withdrawing strong enough for assisting further deprotonation after introduction of the first allyl group thus enabled the two fold allylation. The low yields of substrates examined were mainly due to the premature protonation of the in situ generated carbanions.) S10
11 Preliminary results of assymmetric NAAA reaction. Characterization of structurally novel compounds Methyl 5-(difluoromethylene)-5,6,7,8-tetrahydronaphthalene-2-carboxylate 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 1H), 7.63 (dd, J = 8.3, 1.8 Hz, 1H), 3.91 (s, 3H), 2.83 (t, J = 6.3 Hz, 2H), 2.49 (dddd, J = 8.5, 5.4, 3.2, 2.2 Hz, 2H), 1.86 (qt, J = 6.1, 3.1 Hz, 2H); 19 F NMR (376 MHz, CDCl3) δ (dt, J = 34.8, 3.4 Hz), (d, J = 34.6 Hz); 13 C NMR (101 MHz, CDCl3) δ , (dd, J1 = Hz, J2 = Hz), (dd, J = 6.6, J2 = 1.3 Hz), (dd, J1 = 6.5, J2 = 4.7 Hz), , (t, J = 1.7 Hz), , (d, J = 1.4 Hz), (dd, J = 24.7, 7.8 Hz), 52.04, 30.36, (dd, J1 = 2.6, J2 = 1.7 Hz), (t, J = 1.7 Hz). Methyl 4-(1,1,1-trifluoropent-4-en-2-yl)benzoate Following the general procedure A, 3a was obtained as a colorless oil (38.3 mg, 0.15 mmol, Yield: 99%); 1 H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H), 5.54 (ddt, J = 17.0, 10.2, 6.9 Hz, 1H), (m, 2H), 3.92 (s, 3H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 9.0 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 166.6, (q, J = 2.0 Hz), 133.2, 130.1, 129.8, 129.2, S11
12 126.3 (q, J = Hz), 118.2, 52.1, 50.1 (q, J = 26.6 Hz), 33.2 (q, J = 2.5 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (1,1,1-Trifluoropent-4-en-2-yl)benzonitrile Following the general procedure A, 3b was obtained as a colorless oil (31.7 mg, 0.14 mmol, Yield: 94%); 1 H NMR (400 MHz, CDCl3): δ 7.67 (d, J = 8.6 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 9.3Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 2.0 Hz), 132.7, 132.4, 129.9, (q, J = Hz), 118.7, 118.3, 112.4, 50.1 (q, J = 26.0 Hz), 33.0 (q, J = 2.3 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (Trifluoromethyl)-4-(1,1,1-trifluoropent-4-en-2-yl)benzene Following the general procedure A, 3c was obtained as a colorless oil (33.0 mg, 0.12 mmol, Yield: 82%); 1 H NMR (400 MHz, CDCl3): δ 7.62 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (d, J = 8.0Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.9 Hz), 133.1, (q, J = 32.5 Hz), 129.5, (q, J = Hz), (q, J = 3.8 Hz), (q, J = Hz), 118.4, 50.0 (q, J = 26.8 Hz), 33.1 (q, J = 2.4 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (4-(1,1,1-Trifluoropent-4-en-2-yl)phenyl)ethan-1-one Following the general procedure B, 3d was obtained as a colorless oil (24.3 mg, 0.10 mmol, Yield: 67%); 1 H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 9.5 Hz, 2H), 7.39 (d, J = 9.3 Hz, 2H), (m, 1H), 5.00 (dd, J1 = 16.4 Hz, J2 = 1.8 Hz, 2H), (m, 1H), (m, 1H), (m, 1H), 2.61 (s, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 197.5, (q, J = 1.8 Hz),137.0, 133.3, 129.4, 128.6, (q, J = Hz), 118.3, 50.0 (q, J = 26.2 Hz), 33.1 (q, J = 2.6 Hz), 26.6 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Nitro-2-(1,1,1-trifluoropent-4-en-2-yl)benzene Following the general procedure A, 3e was obtained as a colorless oil (29.8 mg, 0.12 mmol, Yield: 81%); 1 H NMR (400 MHz, CDCl3) δ 7.86 (dd, J = 8.1, 1.3 Hz, 1H), (m, 2H), 7.49 (ddd, J = 8.1, 6.8, 2.1 Hz, 1H), 5.62 (ddt, J = 17.1, 10.1, 6.9 Hz, 1H), (m, 2H), 4.39 (dqd, J = 10.1, 8.9, 5.0 Hz, 1H), 2.86 (dddt, J = 14.4, 6.5, 5.1, 1.5 Hz, 1H), 2.66 (dddt, J = 14.5, 10.1, 7.6, 1.2 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 151.1, 132.8, 132.6, (q, J = 1.5 Hz), 129.0, (q, J = 2.2 Hz), (q, J = Hz), 124.7, 118.7, 42.6 (q, J = 27.2 Hz), 33.5 (q, J = 2.4 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: S12
13 Methyl 2-(1,1,1-trifluoropent-4-en-2-yl)benzoate Following the general procedure A, 3f was obtained as a colorless oil (29.4 mg, 0.11 mmol, Yield: 78%); 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H), 7.37 (ddd, J = 7.9, 5.4, 3.3 Hz, 1H), 5.63 (ddt, J = 17.0, 10.2, 6.9 Hz, 1H), (m, 3H), 3.91 (s, 3H), 2.82 (dddt, J = 14.4, 6.5, 5.1, 1.4 Hz, 1H), 2.65 (dddt, J = 14.4, 10, 7.3, 1.2 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 9.2 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 167.8, (q, J = 2.1 Hz), 133.7, 132.1, 131.3, 130.7, (q, J = 1.5 Hz), 127.7, (q, J = Hz), 117.7, 52.3, 42.8 (q, J = 26.4 Hz), 33.7 (q, J = 2.4 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Methyl 5,5,5-trifluoro-2-methylene-4-(pyridin-2-yl)pentanoate Following the general procedure B, 3g was obtained as a colorless oil (19.3 mg, 0.08 mmol, Yield: 51%); 1 H NMR (400 MHz, CDCl3): δ 8.62 (d, J = 4.4 Hz, 1H), 7.66 (td, J1 = 7.8 Hz, J2 = 1.8 Hz, 1H), (m, 2H), 6.08 (s, 1H), 5.46 (s, 1H), (m, 1H), 3.74 (s, 3H), 3.09 (s, 1H), 3.07 (d, J = 1.3 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 9.0 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.8, 154.0(q, J = 2.0 Hz), 149.6, 136.6, 135.8, 128.6, (q, J = Hz), 124.5, 123.0, 52.0, 50.5 (q, J = 26.2 Hz), 31.0 (q, J = 2.4 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: 260, Nitro-2-(1,1,1-trifluoro-4-methylpent-4-en-2-yl)benzene Following the general procedure B, 3h was obtained as a colorless oil (35.8 mg, 0.13 mmol, Yield: 92%); 1 H NMR (400 MHz, CDCl3) δ 7.85 (dd, J = 8.1, 1.2 Hz, 1H), (m, 2H), 7.48 (ddd, J = 8.6, 6.6, 2.2 Hz, 1H), 4.72 (hept, J = 1.5 Hz, 1H), (m, 2H), 2.78 (dd, J = 14.4, 4.9 Hz, 1H), 2.67 (ddd, J = 14.4, 10.7, 0.9 Hz, 1H), 1.69 (s, 1H) ppm. 19 F NMR (376 MHz, CDCl3) δ (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 151.1, 139.8, 132.7, (q, J = 1.1 Hz), 129.0, (q, J = 2.0 Hz), (q, J = Hz), 124.8, 114.5, 41.0 (q, J = 26.8 Hz), 37.0 (q, J = 2.3 Hz), 21.8 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Methyl 2-(1,1,1-trifluoropent-4-en-2-yl)benzoate Following the general procedure B, 3i was obtained as a colorless oil (37.9 mg, 0.14 mmol, Yield: 93%); 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H), 7.37 (ddd, J = 7.9, 5.4, 3.3 Hz, 1H), 5.63 (ddt, J = 17.0, 10.2, 6.9 Hz, 1H), (m, 3H), 3.91 (s, 3H), 2.82 (dddt, J = 14.4, 6.5, 5.1, 1.4 Hz, 1H), 2.65 (dddt, J = 14.4, 10, 7.3, 1.2 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 9.2 Hz, 3F); 13 C NMR (101 MHz, CDCl3) δ 167.9, 140.8, (q, J = 2.1 Hz), 131.9, 131.3, 130.7, (q, J = 1.0 Hz), 127.7, (q, J = Hz), 113.7, 52.3, 41.2 (q, J = 26.4 Hz), 37.1 (q, J = 2.2 Hz), 22.0 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: S13
14 Methyl 4-(1,1,1-trifluoro-4-methylpent-4-en-2-yl)benzoate Following the general procedure B, 3j was obtained as a colorless oil (37.9 mg, 0.14 mmol, Yield: 93%); 1 H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H), 4.68 (s, 1H), 4.57 (s, 1H), 3.91 (s, 3H), 3.54 (dqd, J = 11.2, 9.1, 4.2 Hz, 1H), 2.75 (dd, J = 14.5, 4.2 Hz, 1H), 2.63 (dd, J = 14.2, 11.4 Hz, 1H), 1.62 (s, 3H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 9.0 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 166.6, 140.1, (q, J = 2.0 Hz), 130.1, 129.7, 129.2, (q, J = Hz), 114.2, 52.1, 48.5 (q, J = 26.8 Hz), 36.8 (q, J = 2.3 Hz), 22.0 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (1,1,1-Trifluoro-4-methylpent-4-en-2-yl)benzonitrile Following the general procedure B, 3k was obtained as a colorless oil (34.4 mg, 0.14 mmol, Yield: 96%); 1 H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 4.70 (s, 1H), 4.56 (s, 1H), 3.55 (dddd, J = 15.6, 13.0, 8.9, 4.1 Hz, 1H), 2.75 (dd, J = 14.5, 4.2 Hz, 1H), 2.61 (dd, J = 14.5, 11.4 Hz, 1H), 1.63 (s, 3H) ppm; 19 F NMR (376 MHz, CDCl3) δ (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ (q, J = 2.0 Hz),138.6, 131.3, 128.9, (q, J = Hz), 117.3, 113.5, 111.3, 47.5 (q, J = 26.8 Hz), 35.6 (q, J = 2.3 Hz), 20.9 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Nitro-3-(1,1,1-trifluoro-4-methylpent-4-en-2-yl)benzene Following the general procedure B, 3l was obtained as acolorless oil (23.3 mg, 0.09 mmol, Yield:60%); 1 H NMR(400 MHz, CDCl3): δ (m, 2H), 7.63 (d, J = 7.9 Hz, 1H),7.55 (t, J = 9.1 Hz, 1H), 4.71 (s, 1H), 4.60 (s, 1H), (m, 1H), (m, 1H), (m, 1H), 1.64 (s, 3H) 19 F NMR (376MHz, CDCl3): δ-69.7 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz,CDCl3): δ 148.3, 139.5, (q, J = 1.8 Hz), 135.3, 139.6, (q, J = Hz), 124.1, 123.3, 114.8, 48.0 (q, J = 27.4 Hz), 36.5 (q, J = 2.2 Hz), 21.9ppm; HRMS (ESI, m/z):calculated for [M+H]+: found: Methyl 5,5,5-trifluoro-2-methylene-4-(2-nitrophenyl)pentanoate Following the general procedure B, 3m was obtained as a colorless oil (32.0 mg, 0.11 mmol, Yield: 74%); 1 H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 7.8 Hz, 1H), (m, 2H), (m, 1H), 6.12 (s, 1H), 5.41 (s, 1H), (m, 1H), 3.77 (s, 3H), 3.19 (dd, J1 =14.2 Hz, J2 = 4.5 Hz, 1H), 2.84(dd, J1 =14.2 Hz, J2 = 10.5 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.4, 151.3, 135.2, 132.7, (q, J = 1.0 Hz), 129.2, 128.7, (q, J = 2.0 Hz), (q, J = Hz), 124.7, 52.2, 41,7 (q, J = 27.6 Hz), 32.2 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: S14
15 4-(1,1,1-Trifluoro-4-phenylpent-4-en-2-yl)benzonitrile Following the general procedure B, 3n was obtained as a colorless oil (33.8 mg, 0.11 mmol, Yield: 75%); 1 H NMR (400 MHz, CDCl3): δ 7.58 (d, J = 8.4 Hz, 2H), (m, 3H), (m, 4H), 5.13 (s, 1H), 4.87 (s, 1H), (m, 2H), 2.92 (dd, J1 = 15.3 Hz, J2 = 12.3 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.7 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 143.3, (q, J = 1.9 Hz), 139.2, 132.2, 129.9, 128.7, 128.1, (q, J = Hz), 126.2, 118.4, 116.6, 112.2, 48.6 (q, J = 26.7 Hz), 35.2 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (1,1,1-Trifluoro-4-(4-fluorophenyl)pent-4-en-2-yl)benzonitrile Following the general procedure B, 3o was obtained as a colorless oil (42.2 mg, 0.14 mmol, Yield: 92%); 1 H NMR (400 MHz, CDCl3): δ 7.60 (d, J = 8.4 Hz, 2H), (m, 4H), (m, 2H), 5.09 (s, 1H), 4.87 (s, 1H), (m, 2H), 2.92 (dd, J1 = 14.4 Hz, J2 = 11.2 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.9 Hz, 3F), (s,1f) ppm; 13 C NMR (100 MHz, CDCl3): δ 163.8, 161.3, 142.3, (q, J = 1.1 Hz), (d, J = 3.3 Hz), 132.3, 129.9, (d, J = 8.0 Hz),126.2 (q, J = Hz), 118.3, 116.7, (d, J = 17.8 Hz), 112.3, 48.5 (q, J = 26.7 Hz), 35.2 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (1,1,1-Trifluoro-4-methylene-6-phenylhex-5-yn-2-yl)benzonitrile Following the general procedure B, 3p was obtained as a colorless oil (22.6 mg, 0.07 mmol, Yield: 46%); 1 H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.6 Hz, 2H), (m, 2H), (m, 3H), 5.35 (s, 1H), 5.18 (s, 1H), (m, 1H), 3.02 (dd, J1 =13.8 Hz, J2 = 3.5 Hz, 1H), 2.74(dd, J1 =13.8 Hz, J2 = 11.5 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.8Hz, 3F) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.8Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.7Hz), 132.3, 131.5, 130.0, 128.7, 128.4, 126.3, (q, J = Hz), 124.7, 122.4, 118.3, 112.4, 91.0, 87.6, 50.0 (q, J = 21.5 Hz), 36.7 (q, J = 2.0 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-1-Nitro-2-(1,1,1-trifluoro-5-phenylpent-4-en-2- yl)benzene Following the general procedure B, 3q was obtained as a colorless oil (33.7 mg, 0.10 mmol, Yield: 70%); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), (m, 1H), (m, 5H), 6.36 (d, J = 15.8 Hz, 1H), 6.00 (dt, J1 = 15.8 Hz, J2 = 7.3 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (q, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.1, 136.7, 133.6, 132.8, (q, J = 1.4 Hz), 129.1, (q, J = 2.1 Hz), 128.5, 127.5, 126.2, (q, J = Hz) 124.8, 124.0, 42.9 (q, J = 26.9 Hz), 33.0 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: S15
16 (E)-1-nitro-2-(1,1,1-trifluoro-5-(4-fluorophenyl)pent-4-en-2-yl)benzene Following the general procedure B, 3r was obtained as a colorless oil (30.1 mg, mmol, Yield: 59%); 1 H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.8 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 2H), 6.32 (d, J = 15.6 Hz, 1H), 5.91 (dt, J1 = 14.8 Hz, J2 = 7.0 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ-68.0 (d, J = 9.0 Hz, 3F), (m, 1F) ppm; 13 C NMR (100 MHz, CDCl3): δ 163.5, 161.1, 151.1, 132.8, 132.5, (q, J = 1.6 Hz), 129.1, (q, J = 1.8 Hz), 127.7, 127.6, (q, J = Hz), 124.8, (q, J = 2.3 Hz), 115.5, 115.3, 43.1 (q, J = 27.8 Hz), 33.0(q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: (E)-1-(5-(4-chlorophenyl)-1,1,1-trifluoropent-4-en-2-yl)-2- nitrobenzene Following the general procedure B, 3s was obtained as a colorless oil (31.6 mg, 0.09 mmol, Yield: 64%); 1 H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 8.5 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H), (m, 2H), (m, 3H), 6.37 (d, J = 14.7 Hz, 1H), 5.88 (dt, J1 =14.1 Hz, J2 = 7.7 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.7 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 2.0 Hz), 136.5, 133.7, 132.5, 129.9, 128.6, 127.7, 126.1, (q, J = Hz), 124.1, 118.3, 112.5, 50.0 (q, J = 25.6 Hz), 32.4 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+Na] + : , found: (E)-methyl4-(1,1,1-trifluoro-5-(4-(trifluoromethyl)phenyl)pent-4-en- 2yl)benzoate Following the general procedure B, 3t was obtained as a colorless oil (33.6 mg, mmol, Yield: 56%); 1 H NMR (400 MHz, CDCl3): δ 8.05 (d, J = 8.5 Hz, 2H), 7.49 (d, J = 7.9 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.30 (d, J = 7.9 Hz, 2H), 6.42 (d, J = 16.1 Hz, 1H), 6.00 (dt, J1 = 15.9 Hz, J2 = 7.6 Hz, 1H), 3.92 (s, 3H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.5, 140.1, (q, J = 1.7 Hz), 132.1, 130.3, (q, J = 32.0 Hz), 130.0, 129.1,127.5, 126.3, (q, J = Hz), 125.5(q, J = 3.9 Hz), (q, J = Hz), 52.2, 50.3 (q, J = 25.9 Hz), 32.6 (q, J = 2.9 Hz),ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: (E)-4-(1,1,1-trifluoro-5-(4-(trifluoromethyl)phenyl)pent-4-en-2- yl)benzonitrile Following the general procedure B, 3u was obtained as a colorless oil (36.8 mg, 0.1 mmol, Yield: 66%); 1 H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.4 Hz, 2H), 7.51(d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 7.03 S16
17 (d, J = 8.4 Hz, 2H), 6.42 (d, J = 15.7 Hz, 1H), 6.00 (dt, J1 = 16.1 Hz, J2 = 5.9 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (d, J = 8.5 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.9 Hz), (q, J = 1.9 Hz), 132.6, 132.5, 129.9, (q, J = 32.6 Hz),126.9, 126.3, (q, J = 280.3Hz), (q, J = 3.9 Hz), (q, J = 272.4Hz),118.2, 112.6, 50.3(q, J = 26.8 Hz), 32.5 (q, J = 2.3 Hz) ppm; HRMS (ESI, m/z): calculated for [M+Na] + : found: (E)-methyl 2-(1,1,1-trifluoro-5-(4-(trifluoromethyl)phenyl)pent-4-en-2- yl)benzoate Following the general procedure B, 3v was obtained as a colorless oil (39.5 mg, 0.1 mmol, Yield: 65%); 1 H NMR (400 MHz, CDCl3): δ 7.91 (dd, J1 = 7.9 Hz, J2 = 0.8 Hz, 1H), (m, 2H), 7.49 (d, J = 8.4 Hz, 2H), (m, 1H), 7.30 (d, J = 8.2 Hz, 2H), 6.38 (d, J = 16.0 Hz, 1H), 6.14 (dt, J1 = 14.3 Hz, J2 = 6.9 Hz, 1H), (m, 1H), 3.87 (s, 3H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 167.8, (q, J = 1.6 Hz), (q, J = 2.7 Hz), 132.2, 131.4, 131.2, 130.9, (q, J = 32.5 Hz), (q, J = 1.4 Hz), 128.3, (q, J = Hz), 127.9, 126.2, (q, J = 3.5 Hz), (q, J = Hz), 52.3, 43.1 (q, J = 26.0 Hz), 33.3 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: Methyl (E)-4-(5,5,5-trifluoro-4-(2-nitrophenyl)pent-1-en-1-yl)benzoate Following the general procedure B, 3w was obtained as a colorless oil (27.3 mg, mmol, Yield: 48%); 1 H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 1H), 7.66 (d, J = 4.1 Hz, 2H), (m, 1H), 7.28 (d, J = 8.3 Hz, 2H), 6.41 (d, J = 15.4 Hz, 1H), 6.14 (dt, J1 = 15.4 Hz, J2 = 7.5 Hz, 1H), (m, 1H), 3.89 (s, 3H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ-68.0 (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.8, 151.1, 141.1, 132.9, 132.8, 129.9, (q, J = 1.8 Hz), 129.2, 129.1, (q, J = 2.0 Hz), 126.9, 126.1, 126.0(q, J = Hz), 124.8, 52.0, 42.9(q, J = 27.0 Hz), 33.1 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: (E)-1-Nitro-2-(1,1,1-trifluoro-5-(4-(trifluoromethyl)phenyl)pent-4-en-2- yl)benzene Following the general procedure B, 3x was obtained as a colorless oil (53.1 mg, 0.14 mmol, Yield: 91%); 1 H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 4.1 Hz, 2H), 7.50 (d, J = 7.9 Hz, 3H), 7.32 (d, J = 8.0 Hz, 2H), 6.39 (d, J = 16.4 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.0, (q, J = 1.2 Hz), 132.9, 132.4, (q, J = 32.0 Hz), 129.2, (q, J = 1.4 Hz), (q, J = 2.1 Hz), 126.9, 126.3, 126.0(q, J = Hz), (q, J = 3.7 Hz), S17
18 124.8, (q, J = Hz), 42.9 (q, J = 27.1 Hz), 33.1 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-4-(5,5,5-Trifluoro-4-(2-nitrophenyl)pent-1-enyl)benzonitrile Following the general procedure B, 3y was obtained as a colorless oil (22.9 mg, 0.7 mmol, Yield: 48%); 1 H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.2 Hz, 1H), (m, 2H), (m, 3H), 7.31 (d, J = 8.2 Hz, 2H), 6.39 (d, J = 15.8 Hz, 1H), 6.16 (dt, J1 = 15.8 Hz, J2 = 7.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.0, 141.0, 133.0, 132.4, 132.1, 129.3, (q, J = 1.5 Hz), 128.3, (q, J = 2.0 Hz), 126.7, (q, J = Hz), 124.9, 118.8, 110.9, 42.9 (q, J = 27.1 Hz), 33.1 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-1-Methoxy-2-(5,5,5-trifluoro-4-(2-nitrophenyl)pent-1-enyl)benzene Following the general procedure B, 3z was obtained as a colorless oil (40.0 mg, 0.11 mmol, Yield: 76%); 1 H NMR (400 MHz, CDCl3): δ 7.84 (dd, J1 =8.1 Hz, J2 = 0.9 Hz, 1H), (m, 2H), (m, 1H), 7.23 (dd, J1 =7.6 Hz, J2 = 1.6 Hz, 1H), 7.17 (td, J1 =8.1 Hz, J2 = 0.9 Hz, 1H), 6.85 (t, J = 7.4 Hz, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.66 (d, J = 15.9 Hz, 1H), 5.97 (dt, J1 =14.7 Hz, J2 = 7.1 Hz, 1H), (m, 1H), 3.78 (s, 3H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 156.5, 151.1, 132.8, (q, J = 1.4 Hz), 129.0, (q, J = 2.1 Hz), 128.6, 128.6, 126.8, (q, J = Hz), 125.9, 124.7, 124.7, 120.6, 110.8, 55.4, 43.0 (q, J = 26.8 Hz), 33.3 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-1-Nitro-2-(1,1,1-trifluoro-5-(3-methoxyphenyl)pent-4-en-2-yl)benzene Following the general procedure B, 3aa was obtained as a colorless oil (34.8 mg, 0.10 mmol, Yield: 66%); 1 H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.3 Hz, 1H), (m, 2H), (m, 1H), 7.17 (t, J = 7.8 Hz, 1H), 6.82 (d, J = 7.7 Hz, 1H), (m, 2H), 6.33 (d, J = 15.7 Hz, 1H), 5.99 (dt, J1 = 15.7, J2 = 7.2 Hz, 1H), (m, 1H), 3.78 (s, 3H), (m,1h), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 159.7, 151.1, 138.2, 133.5, 132.8, 129.5, (q, J = 1.4 Hz), 129.1, (q, J = 2.0 Hz), (q, J = Hz),124.8, 124.4, 118.8, 113.1, 111.6, 55.2, 42.9 (q, J = 26.9 Hz), 32.9 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: S18
19 (E)-1-(5,5,5-Trifluoro-4-(2-nitrophenyl)pent-1-enyl)naphthalene Following the general procedure B, 3ab was obtained as a colorless oil (27.8 mg, 0.8 mmol, Yield: 50%); 1 H NMR (400 MHz, CDCl3): δ 7.84 (d, J = 8.2 Hz), (m, 2H), (m, 2H), 7.66 (t, J = 7.5 Hz, 1H), (m, 3H), (m, 2H), 7.06 (d, J = 15.5 Hz, 1H), 6.00 (dt, J1 =15.5 Hz, J2 = 7.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.2, 134.6, 133.4, 132.8, 131.4, 130.9, (q, J = 2.4 Hz), 129.1, (q, J = 2.1 Hz), 128.5, 127.9, 127.3, (q, J = Hz), 125.9, 125.7, 125.6, 124.8, 123.9, 123.6, 42.9 (q, J = 27.0 Hz), 33.2 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-3-(5,5,5-Trifluoro-4-(2-nitrophenyl)pent-1-enyl)pyridine Following the general procedure B, 3ac was obtained as a colorless oil (31.0 mg, 0.10 mmol, Yield: 64%); 1 H NMR (400 MHz, CDCl3): δ (m, 2H), 7.84 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 4.3 Hz, 2H), 7.56 (d, J = 7.8 Hz, 1H), (m, 1H), 7.19 (dd, J1 = 7.7 Hz, J2 = 4.9 Hz, 1H), 6.36 (d, J = 15.9 Hz, 1H), 6.08 (dt, J1 =15.9 Hz, J2 = 7.2 Hz, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.1, 148.5, 148.0, 132.9, 132.6, 130.1, 129.2, (q, J = 1.9 Hz), 126.7, (q, J = Hz), 124.8, (q, J = 2.3 Hz), 42.9 (q, J = 26.0 Hz), 33.1 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (E)-1-Nitro-2-(1,1,1-trifluorohepta-4,6-dien-2-yl)benzene Following the general procedure B, 3ad was obtained as a mixture of stereoisomers with L:B as 3:1 (33.0 mg, 0.12 mmol, Yield: 81%); 1 H NMR (400 MHz, CDCl3): δ (m, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.9 Hz), 136.6, 136.2, 134.6, 132.8, (q, J = 1.4 Hz), 129.0, 127.9, (q, J = Hz), 124.8, 116.9, 42.8 (q, J = 27.9 Hz), 32.4 (q, J = 2.2 Hz) ppm; HRMS (ESI, m/z): calculated for [M+Na] + : , found: (E)-1-(5-cyclohexyl-1,1,1-trifluoropent-4-en-2-yl)-2-nitrobenzene Following the general procedure B, 3ae was obtained as a colorless oil (38.5 mg, 0.11 mmol, Yield: 78%); 1 H NMR (400 MHz, CDCl3): δ (dd, J1 = 8.2 Hz, J2 = 1.1 Hz, 2H), (m, 2H), 7.46 (td, J1 = 7.2 Hz, J2 = 2.2 Hz, 2H), 5.29 (dd, J1 = 6.9 Hz, J2 = 6.6 Hz, 1H), 5.12 (dt, J1 = 16.0 Hz, J2 = 7.4 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 4H), (m, 1H), (m, 3H), (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ (d, J = 9.4 Hz, 3F) ppm; 13 C NMR (100 S19
20 MHz, CDCl3): δ 151.3, 141.2, 132.6, (q, J = 1.5 Hz), (q, J = 2.0 Hz), 128.8, (q, J = Hz), 124.5, 121.2, 43.2 (q, J = 26.9 Hz), 40.4, 32.7 (q, J = 2.2 Hz), 32.6, 32.6, 26.0, 25.8, 25.8 ppm; HRMS (ESI, m/z): calculated for [M+H] + : calculated for [M+H] + : found: (E)-1-nitro-4-(1,1,1-trifluoro-2-methyl-5-(4-(trifluoromethyl)phenyl) pent-4-en-2-yl)benzene Following the general procedure B, 3af was obtained as a yellow solid (58.9 mg, 0.15 mmol, Yield: 99%); 1 H NMR (400 MHz, CDCl3): δ 8.25(d, J = 8.3 Hz, 2H), 7.70(d, J = 8.0 Hz, 2H), 7.49 (d, J = 7.5 Hz, 2H), 7.30 (d, J = 7.1 Hz, 2H), 6.51 (d, J = 15.1 Hz, 1H), 5.86 (dt, J1 = 15.4 Hz, J2 = 6.5 Hz, 1H), 3.19 (dd, J1 = 7.1 Hz, J2 = 6.9 Hz, 1H), 2.82 (dd, J1 = 8.9 Hz, J2 = 8.5 Hz, 1H), 1.67 (s, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.5, 144.7, (q, J = 1.3 Hz), 133.8, (q, J = 32.4 Hz), 129.1, (q, J = Hz),126.3, (q, J = 3.9 Hz), 125.1, (q, J = Hz),123.5, 48.1 (q, J = 25.2 Hz), 38.7 (q, J = 1.7 Hz), 18.9 (q, J = 2.0 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: Nitro-4-(1,1,1-trifluoro-2-methylpent-4-en-2-yl)benzene Following the general procedure B, 3ag was obtained as a colorless oil (38.5 mg, 0.15 mmol, Yield: 99%); 1 H NMR (400 MHz, CDCl3): δ 8.23 (d, J = 9.0 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), (m, 1H), 5.13 (dd, J1 = 17.0 Hz, J2 = 1.2 Hz, 1H), 5.06 (d, J = 10.1 Hz, 1H), 3.02 (dd, J1 = 14.3 Hz, J2 = 6.2 Hz, 1H), 2.62 (dd, J1 = 14.3 Hz, J2 = 6.2 Hz, 1H), 1.62 (s, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s,3f) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.4, 144.9, 130.8, (q, J = 1.1 Hz), (q, J = Hz), 123.3, 120.3, 47.7 (q, J = 24.3 Hz), 39.3 (q, J = 2.0 Hz), 18.7 (q, J = 2.5 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Methyl 4-(1,1,1-trifluoro-2-methylpent-4-en-2-yl)benzoate Following the general procedure B, 3ah was obtained as a colorless oil (38.8 mg, 0.14 mmol, Yield: 95%); 1 H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 8.7 Hz, 2H), 7.54 (d, J = 8.3 Hz, 2H), (m, 1H), 5.10 (dq, J1 = 17.1 Hz, J2 = 1.7 Hz, 1H), 5.02 (d, J = 9.4 Hz, 1H), 3.92 (s, 3H), 3.02 (dd, J1 = 14.2 Hz, J2 = 6.0 Hz, 1H), 2.56 (dd, J1 = 14.2 Hz, J2 = 6.0 Hz, 1H), 1.57 (s, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ -74.8(s,3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.7, 142.6, 131.5, 129.5, 129.4, (q, J =0.9 Hz), (q, J = Hz), 119.6, 52.1, 47.4 (q, J = 24.0 Hz), 39.3 (d, J = 2.0 Hz), 18.6 (d, J = 2.4 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: (trifluoromethyl)-4-(3-(trifluoromethyl)hex-5-en-3-yl)benzene Following the general procedure B, 3ai was obtained as a colorless oil (24.4 mg, 0.08 mmol, Yield: 55%); 1 H NMR (400 MHz, CDCl3): δ 7.63 (d, J = 8.6 Hz, 2H), 7.58 (d, J = 8.6 Hz, S20
21 2H), (m, 1H), 5.17 (dd, J1 = 17.0 Hz, J2 = 1.6 Hz, 1H), 5.12 (dd, J1 = 10.2 Hz, J2 = 1.5 Hz, 1H), 2.92 (dd, J1 = 15.0 Hz, J2 = 6.1 Hz, 1H), 2.73 (dd, J1 = 14.9 Hz, J2 = 6.1 Hz, 1H), (m, 2H), 0.89 (t, J = 7.4 Hz, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F), (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 141.5, 132.2, (q, J = 32.7 Hz), (q, J = 1.1 Hz), (q, J = Hz), (q, J = 4.0 Hz), (q, J = Hz), 119.1, 50.8 (q, J =22.7 Hz), 36.9 (q, J = 2.1 Hz), 24.9 (q, J =1.8 Hz), 8.0 (q, J =1.0 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : found: Methyl 5-(2-(methoxycarbonyl)allyl)-5-(trifluoromethyl)-5,6,7,8-tetrahydronaphthalene-2-carboxylate Following the general procedure B, 3aj was obtained as a colorless oil (27.3 mg, 0.08 mmol, Yield: 51%); 1 H NMR (400 MHz, CDCl3): δ (m, 2H), 7.62 (d, J = 8.4 Hz, 1H), 6.13 (d, J = 0.9 Hz, 1H), 5.33 (s, 1H), 3.91 (s, 3H), 3.63 (s, 3H), 3.06 (q, J = 13.0 Hz, 2H), 2.79 (t, J = 6.7 Hz, 2H), (m, 1H), (m, 2H), (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 167.7, 166.7, 139.6, 137.6, 135.7, 130.8, 129.6, 129.2, (q, J = 2.4 Hz), (q, J = Hz), 126.7, 52.1, 52.0, 47.7 (q, J = 22.9 Hz), 36.6 (q, J = 1.8 Hz), 30.2, 28.4 (q, J = 1.8 Hz), 18.9 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Ethyl 5-methyl 2-methyl-4-methylene-2-(trifluoromethyl)pentanedioate Following the general procedure B, 3ak was obtained as a colorless oil (31.4 mg, 0.12 mmol, Yield: 78%); 1 H NMR (400 MHz, CDCl3): δ 6.31 (d, J = 1.0 Hz, 1H), 5.65 (d, J = 0.8 Hz, 1H), (m, 2H), 3.75(s, 3H), 3.06 (d, J = 13.8 Hz, 1H), 2.77 (d, J = 13.8 Hz, 1H), 1.29 (t, J = 7.1 Hz, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s,3f) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.3Hz), 167.1, 134.9, 129.7, (q, J = Hz), 61.9, 52.5 (q, J = 26.8 Hz), 52.1, 33.8 (q, J = 2.2 Hz), 16.1 (q, J = 2.2 Hz), 13.9 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Ethyl 5-methyl 4-methylene-2-phenyl-2-(trifluoromethyl)-pentanedioate Following the general procedure B, 3al was obtained as a colorless oil (25.3 mg, 0.08 mmol, Yield: 51%); 1 H NMR (400 MHz, CDCl3): δ (m, 3H), (m, 2H), 6.19 (d, J = 1.1 Hz, 1H), 5.47 (d, J = 1.1 Hz, 1H), (m, 1H), (m, 1H), 3.68 (s, 3H), 3.62 (dd, J1 = 14.4 Hz, J2 = 0.8 Hz, 1H), 3.22 (d, J = 14.4 Hz, 1H), 1.28 (t, J = 7.1 Hz, 3 H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ (q, J = 1.3 Hz), 137.4, 135.4, 134.2, 129.2, 128.4, 128.3, 128.0, (q, J = Hz), 62.1, 61.6 (q, J = 24.5 Hz), 52.0, 33.4 (q, J = 1.2 Hz), 13.8 ppm; HRMS(ESI, m/z): calculated for [M+H] + : , found: S21
22 Following the general procedure B, 3am was obtained as a colorless oil (39.2 mg, 0.12 mmol, Yield: 80%); 1 H NMR (400 MHz, CDCl3): δ (m, 2H), (m, 3H), 6.18 (s, 1H), 5.39 (s, 1H), 3.67 (s, 3H), 3.48 (s, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 6F) ppm; 13 C NMR (100 MHz, CDCl3): δ 167.2, 133.3, 130.1, 129.2, 129.0, (m), 128.5, (q, J = Hz), (m), 52.1, (m) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Nitro-4-(4-(trifluoromethyl)octa-1,7-dien-4-yl)benzene Following the general procedure A, 3an was obtained as a colorless oil (40.7 mg, 0.14 mmol, Yield: 95%); 1 H NMR (400 MHz, CDCl3): δ 8.22 (d, J = 8.9 Hz, 2H), 7.67 (d, J = 8.7 Hz, 2H), (m, 2H), (m, 4H), 2.93 (m, 2H), 2.80 (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.2, 144.4, 131.3, (q, J = 1.5 Hz), (q, J = Hz), 123.3, 120.0, 50.9 (q, J = 22.9 Hz), 37.1 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Methyl 5,5,5-trifluoro-2-methylene-4-phenyl-4-(trifluoromethyl)pentaneate 4,4'-((1E,6E)-4-(4-Nitrophenyl)-4-(trifluoromethyl)octa-1,6-diene-1,8- diyl)bis(methoxybenzene) Following the general procedure A, 3ao was obtained as a colorless oil (46.3 mg, 0.09 mmol, Yield: 62%); 1 H NMR (400 MHz, CDCl3): δ 8.24 (d, J = 8.8 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 8.7 Hz, 4H), 6.81 (d, J = 8.9 Hz, 4H), 6.44 (d, J = 15.0 Hz, 2H), 6.86 (dt, J1 =15.0 Hz, J2 = 8.6 Hz, 2H), 3.79 (s,6h), (m, 2H), (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 159.3, 147.3, 144.6, 134.3, 129.6, 129.6, (q, J = 285.6Hz), 127.3,123.4, 120.4, 114.0, 55.3, 51.6 (q, J = 23.8Hz), 36.6 ppm; HRMS (ESI, m/z): calculated for [M+H] + : , found: Reference [1] M. Hu, C. Ni, L. Li, Y. Han, J. Hu. J. Am. Chem. Soc. 2012, 134, [2] P. Tian, C. Feng, T.-P. Loh, Nat. commun. 2015, 6, S22
23 1H, 19F and 13C NMR spectra of structurally novel compounds S23
24 S24
25 S25
26 S26
27 S27
28 S28
29 S29
30 S30
31 S31
32 S32
33 S33
34 S34
35 S35
36 S36
37 S37
38 S38
39 S39
40 S40
41 S41
42 S42
43 S43
44 S44
45 S45
46 S46
47 S47
48 S48
49 S49
50 S50
51 S51
52 S52
53 S53
54 S54
55 S55
56 S56
57 S57
58 S58
59 S59
60 S60
61 S61
62 S62
63 S63
Synthesis of Trifluoromethylated Naphthoquinones via Copper-Catalyzed. Cascade Trifluoromethylation/Cyclization of. 2-(3-Arylpropioloyl)benzaldehydes
Supporting Information to Synthesis of Trifluoromethylated Naphthoquinones via Copper-Catalyzed Cascade Trifluoromethylation/Cyclization of 2-(3-Arylpropioloyl)benzaldehydes Yan Zhang*, Dongmei Guo, Shangyi
More informationCarbonylative Coupling of Allylic Acetates with. Arylboronic Acids
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Carbonylative Coupling of Allylic Acetates with Arylboronic Acids Wei Ma, a Ting Yu, Dong Xue,*
More informationSupporting Information
Supporting Information Total Synthesis of (±)-Grandilodine B Chunyu Wang, Zhonglei Wang, Xiaoni Xie, Xiaotong Yao, Guang Li, and Liansuo Zu* School of Pharmaceutical Sciences, Tsinghua University, Beijing,
More informationAmide Directed Cross-Coupling between Alkenes and Alkynes: A Regio- and Stereoselective Approach to Substituted (2Z,4Z)-Dienamides
Supporting Information For the article entitled Amide Directed Cross-Coupling between Alkenes and Alkynes: A Regio- and Stereoselective Approach to Substituted (2Z,4Z)-Dienamides Keke Meng, Jian Zhang,*
More informationIridium-catalyzed regioselective decarboxylative allylation of. β-ketoacids: efficient construction of γ, δ-unsaturated ketones
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Iridium-catalyzed regioselective decarboxylative allylation of β-ketoacids: efficient construction
More informationSupporting Information
Supporting Information Silver-Mediated Oxidative Trifluoromethylation of Alcohols to Alkyl Trifluoromethyl Ethers Jian-Bo Liu, Xiu-Hua Xu, and Feng-Ling Qing Table of Contents 1. General Information --------------------------------------------------------------------------2
More informationSupporting Information
Supporting Information Synthesis of H-Indazoles from Imidates and Nitrosobenzenes via Synergistic Rhodium/Copper Catalysis Qiang Wang and Xingwei Li* Dalian Institute of Chemical Physics, Chinese Academy
More informationAn Efficient Total Synthesis and Absolute Configuration. Determination of Varitriol
An Efficient Total Synthesis and Absolute Configuration Determination of Varitriol Ryan T. Clemens and Michael P. Jennings * Department of Chemistry, University of Alabama, 500 Campus Dr. Tuscaloosa, AL
More informationSupporting Information
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2016 Supporting Information Synthesis of Biaryl Sultams Using Visible-Light-Promoted Denitrogenative
More informationTetrahydrofuran (THF) was distilled from benzophenone ketyl radical under an argon
SUPPLEMENTARY METHODS Solvents, reagents and synthetic procedures All reactions were carried out under an argon atmosphere unless otherwise specified. Tetrahydrofuran (THF) was distilled from benzophenone
More informationSupporting information for A simple copper-catalyzed two-step one-pot synthesis of indolo[1,2-a]quinazoline
Supporting information for A simple copper-catalyzed two-step one-pot synthesis of indolo[1,2-a]quinazoline Chunpu Li 1,2, Lei Zhang 2, Shuangjie Shu 2 and Hong Liu* 1,2 Address: 1 Department of Medicinal
More informationSynthesis of Glaucogenin D, a Structurally Unique. Disecopregnane Steroid with Potential Antiviral Activity
Supporting Information for Synthesis of Glaucogenin D, a Structurally Unique Disecopregnane Steroid with Potential Antiviral Activity Jinghan Gui,* Hailong Tian, and Weisheng Tian* Key Laboratory of Synthetic
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting Information TEMPO-catalyzed Synthesis of 5-Substituted Isoxazoles from Propargylic
More informationEnantioselective Conjugate Addition of 3-Fluoro-Oxindoles to. Vinyl Sulfone: An Organocatalytic Access to Chiral. 3-Fluoro-3-Substituted Oxindoles
Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to Vinyl Sulfone: An Organocatalytic Access to Chiral 3-Fluoro-3-Substituted Oxindoles Xiaowei Dou and Yixin Lu * Department of Chemistry & Medicinal
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information Palladium-Catalyzed Oxidative Allylation of Bis[(pinacolato)boryl]methane:
More informationThe First Asymmetric Total Syntheses and. Determination of Absolute Configurations of. Xestodecalactones B and C
Supporting Information The First Asymmetric Total Syntheses and Determination of Absolute Configurations of Xestodecalactones B and C Qiren Liang, Jiyong Zhang, Weiguo Quan, Yongquan Sun, Xuegong She*,,
More informationCatalytic Reductive Dehydration of Tertiary Amides to Enamines under Hydrosilylation Conditions
SUPPORTIG IFORMATIO Catalytic Reductive Dehydration of Tertiary Amides to Enamines under Hydrosilylation Conditions Alexey Volkov, a Fredrik Tinnis, a and Hans Adolfsson.* a a Department of Organic Chemistry,
More informationReactions. James C. Anderson,* Rachel H. Munday. School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, UK
Vinyl-dimethylphenylsilanes as Safety Catch Silanols in Fluoride free Palladium Catalysed Cross Coupling Reactions. James C. Anderson,* Rachel H. Munday School of Chemistry, University of Nottingham, Nottingham,
More informationSupporting Material. 2-Oxo-tetrahydro-1,8-naphthyridine-Based Protein Farnesyltransferase Inhibitors as Antimalarials
Supporting Material 2-Oxo-tetrahydro-1,8-naphthyridine-Based Protein Farnesyltransferase Inhibitors as Antimalarials Srinivas Olepu a, Praveen Kumar Suryadevara a, Kasey Rivas b, Christophe L. M. J. Verlinde
More informationEfficient Mono- and Bis-Functionalization of 3,6-Dichloropyridazine using (tmp) 2 Zn 2MgCl 2 2LiCl ** Stefan H. Wunderlich and Paul Knochel*
Efficient Mono- and Bis-Functionalization of 3,6-Dichloropyridazine using (tmp) 2 Zn 2Mg 2 2Li ** Stefan H. Wunderlich and Paul Knochel* Ludwig Maximilians-Universität München, Department Chemie & Biochemie
More informationSupporting Information. Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template
Supporting Information Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template Hua-Jin Xu, Yi Lu, *, Marcus E. Farmer, Huai-Wei Wang, Dan Zhao, Yan-Shang Kang, Wei-Yin Sun, *, Jin-Quan Yu
More informationSupporting Information. Rhodium(III)-Catalyzed Synthesis of Naphthols via C-H Activation. of Sulfoxonium Ylides. Xingwei Li*, Table of Contents
Supporting Information Rhodium(III)-Catalyzed Synthesis of Naphthols via C-H Activation of Sulfoxonium Ylides Youwei Xu,, Xifa Yang,, Xukai Zhou,, Lingheng Kong,, and Xingwei Li*, Dalian Institute of Chemical
More informationIndium Triflate-Assisted Nucleophilic Aromatic Substitution Reactions of. Nitrosobezene-Derived Cycloadducts with Alcohols
Supporting Information Indium Triflate-Assisted ucleophilic Aromatic Substitution Reactions of itrosobezene-derived Cycloadducts with Alcohols Baiyuan Yang and Marvin J. Miller* Department of Chemistry
More informationAccessory Information
Accessory Information Synthesis of 5-phenyl 2-Functionalized Pyrroles by amino Heck and tandem amino Heck Carbonylation reactions Shazia Zaman, *A,B Mitsuru Kitamura B, C and Andrew D. Abell A *A Department
More informationSupporting Information
Supporting Information for Cu-Mediated trifluoromethylation of benzyl, allyl and propargyl methanesulfonates with TMSCF 3 Xueliang Jiang 1 and Feng-Ling Qing* 1,2 Address: 1 Key Laboratory of Organofluorine
More informationRing-Opening / Fragmentation of Dihydropyrones for the Synthesis of Homopropargyl Alcohols
Ring-pening / Fragmentation of Dihydropyrones for the Synthesis of Homopropargyl Alcohols Jumreang Tummatorn, and Gregory B. Dudley, * Department of Chemistry and Biochemistry, Florida State University,
More informationSupporting Information
Supporting Information Construction of Highly Functional α-amino itriles via a ovel Multicomponent Tandem rganocatalytic Reaction: a Facile Access to α-methylene γ-lactams Feng Pan, Jian-Ming Chen, Zhe
More informationSupplementary Note 1 : Chemical synthesis of (E/Z)-4,8-dimethylnona-2,7-dien-4-ol (4)
Supplementary Note 1 : Chemical synthesis of (E/Z)-4,8-dimethylnona-2,7-dien-4-ol (4) A solution of propenyl magnesium bromide in THF (17.5 mmol) under nitrogen atmosphere was cooled in an ice bath and
More informationSupporting Information. Cu(I)-Catalyzed Three-Component Reaction of Diazo. Compound with Terminal Alkyne and Nitrosobenzene for
Supporting Information of Cu(I)-Catalyzed Three-Component Reaction of Diazo Compound with Terminal Alkyne and Nitrosobenzene for the Synthesis of Trifluoromethyl Dihydroisoxazoles Xinxin Lv, Zhenghui Kang,
More informationSilver-catalyzed decarboxylative acylfluorination of styrenes in aqueous media
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Silver-catalyzed decarboxylative acylfluorination of styrenes in aqueous
More informationSuzuki-Miyaura Coupling of Heteroaryl Boronic Acids and Vinyl Chlorides
Suzuki-Miyaura Coupling of Heteroaryl Boronic Acids and Vinyl Chlorides Ashish Thakur, Kainan Zhang, Janis Louie* SUPPORTING INFORMATION General Experimental: All reactions were conducted under an atmosphere
More informationUniversity of Groningen
University of Groningen Palladium-Catalyzed Selective Anti-Markovnikov Oxidation of Allylic Esters Dong, Jia Jia; Fananas-Mastral, Martin; Alsters, Paul L.; Browne, Wesley; Feringa, B.L. Published in:
More informationElectronic Supplementary Material (ESI) for Medicinal Chemistry Communications This journal is The Royal Society of Chemistry 2012
Supporting Information. Experimental Section: Summary scheme H 8 H H H 9 a H C 3 1 C 3 A H H b c C 3 2 3 C 3 H H d e C 3 4 5 C 3 H f g C 2 6 7 C 2 H a C 3 B H c C 3 General experimental details: All solvents
More informationSUPPORTING INFORMATION
SUPPORTING INFORMATION For Synthesis of Fluorenone Derivatives through Palladium-Catalyzed Dehydrogenative Cyclization Hu Li, Ru-Yi Zhu, Wen-Juan Shi, Ke-Han He, and Zhang-Jie Shi* Beijing National Laboratory
More informationFast and Flexible Synthesis of Pantothenic Acid and CJ-15,801.
Fast and Flexible Synthesis of Pantothenic Acid and CJ-15,801. Alan L. Sewell a, Mathew V. J. Villa a, Mhairi Matheson a, William G. Whittingham b, Rodolfo Marquez a*. a) WestCHEM, School of Chemistry,
More informationSYNTHESIS OF A 3-THIOMANNOSIDE
Supporting Information SYNTHESIS OF A 3-THIOMANNOSIDE María B Comba, Alejandra G Suárez, Ariel M Sarotti, María I Mangione* and Rolando A Spanevello and Enrique D V Giordano Instituto de Química Rosario,
More informationIron Catalyzed Cross Couplings of Azetidines: Application to an Improved Formal Synthesis of a Pharmacologically Active Molecule
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Iron Catalyzed Cross Couplings of Azetidines: Application to an Improved Formal Synthesis of a
More informationSupporting Information for Exploration of C H and N H-bond functionalization towards 1-(1,2-diarylindol-3-yl)- tetrahydroisoquinolines
Supporting Information for Exploration of C H and N H-bond functionalization towards 1-(1,2-diarylindol-3-yl)- tetrahydroisoquinolines Michael Ghobrial, Marko D. Mihovilovic and Michael Schnürch* Address:
More informationSynthesis of borinic acids and borinate adducts using diisopropylaminoborane
Synthesis of borinic acids and borinate adducts using diisopropylaminoborane Ludovic Marciasini, Bastien Cacciuttolo, Michel Vaultier and Mathieu Pucheault* Institut des Sciences Moléculaires, UMR 5255,
More informationSUPPLEMENTARY INFORMATION
Supplementary Method Synthesis of 2-alkyl-MPT(R) General information (R) enantiomer of 2-alkyl (18:1) MPT (hereafter designated as 2-alkyl- MPT(R)), was synthesized as previously described 1, with some
More informationDomino reactions of 2-methyl chromones containing an electron withdrawing group with chromone-fused dienes
Domino reactions of 2-methyl chromones containing an electron withdrawing group with chromone-fused dienes Jian Gong, Fuchun Xie, Wenming Ren, Hong Chen and Youhong Hu* State Key Laboratory of Drug Research,
More informationSynergistic Cu/Ir Catalysis. Table of Contents
Supporting Information for Stereodivergent Synthesis of, -Disubstituted -Amino Acids via Synergistic Cu/Ir Catalysis Liang Wei, 1 Qiao Zhu, 1 Shi-Ming Xu, 1 Xin Chang 1 and Chun-Jiang Wang* 1,2 1 College
More informationSupporting Information
Supporting Information N-Heterocyclic Carbene-Catalyzed Chemoselective Cross-Aza-Benzoin Reaction of Enals with Isatin-derived Ketimines: Access to Chiral Quaternary Aminooxindoles Jianfeng Xu 1, Chengli
More informationSupporting Information
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information Palladium-Catalyzed Regio-selective xidative C-H
More informationSupporting Information for. A New Method for the Cleavage of Nitrobenzyl Amides and Ethers
SI- 1 Supporting Information for A ew Method for the Cleavage of itrobenzyl Amides and Ethers Seo-Jung Han, Gabriel Fernando de Melo, and Brian M. Stoltz* The Warren and Katharine Schlinger Laboratory
More informationEfficient Pd-Catalyzed Amination of Heteroaryl Halides
1 Efficient Pd-Catalyzed Amination of Heteroaryl Halides Mark D. Charles, Philip Schultz, Stephen L. Buchwald* Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 Supporting
More informationSupporting Information
Supporting Information Divergent Reactivity of gem-difluoro-enolates towards Nitrogen Electrophiles: Unorthodox Nitroso Aldol Reaction for Rapid Synthesis of -Ketoamides Mallu Kesava Reddy, Isai Ramakrishna,
More informationSupporting Information
Supporting Information Efficient Short Step Synthesis of Corey s Tamiflu Intermediate Nsiama Tienabe Kipassa, Hiroaki kamura, * Kengo Kina, Tetsuo Iwagawa, and Toshiyuki Hamada Department of Chemistry
More informationDual role of Allylsamarium Bromide as Grignard Reagent and a. Single Electron Transfer Reagent in the One-Pot Synthesis of.
Dual role of Allylsamarium Bromide as Grignard Reagent and a Single Electron Transfer Reagent in the One-Pot Synthesis of Terminal Olefins Ying Li, Yuanyuan Hu and Songlin Zhang* Key Laboratory of Organic
More informationSupporting Information
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry Supporting Information General Remarks Most of chemicals were purchased from Sigma-Aldrich, Strem,
More informationSolvent-Controlled Pd(II)-Catalyzed Aerobic Chemoselective. Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination of
Supporting Information Solvent-Controlled Pd(II)-Catalyzed Aerobic Chemoselective Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination of Conjugated Dienes for the Synthesis of Functionalized 1,4-Benzoxazines
More informationfor Brønsted Base-Mediated Aziridination of 2- Alkyl Substituted-1,3-Dicarbonyl Compounds and 2-Acyl-1,4-Dicarbonyl Compounds by Iminoiodanes
10.1071/CH16580_AC CSIRO 2017 Australian Journal of Chemistry 2017, 70(4), 430-435 Supplementary Material for Brønsted Base-Mediated Aziridination of 2- Alkyl Substituted-1,3-Dicarbonyl Compounds and 2-Acyl-1,4-Dicarbonyl
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2017 Supporting Information Lithium Triethylborohydride-Promoted Generation of α,α-difluoroenolates
More informationQile Wang, and Nan Zheng* Department of Chemistry and Biochemistry, University of Arkansas. Fayetteville, Arkansas,
Supporting Information A Photocatalyzed Synthesis of Naphthalenes by Using Aniline as a Traceless Directing Group in [4+2] Annulation of AminoBenzocyclobutenes with Alkynes Qile Wang, and Nan Zheng* Department
More informationhydroxyanthraquinones related to proisocrinins
Supporting Information for Regiodefined synthesis of brominated hydroxyanthraquinones related to proisocrinins Joyeeta Roy, Tanushree Mal, Supriti Jana and Dipakranjan Mal* Address: Department of Chemistry,
More informationSupporting Information for Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers: Approaches to Diazonamide A
Fuerst et al. Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers: Approaches to Diazonamide A S1 Supporting Information for Synthesis of C(3) Benzofuran Derived Bis-Aryl Quaternary Centers:
More informationSupporting Information
Supporting Information Lewis acid-catalyzed intramolecular condensation of ynol ether-acetals. Synthesis of alkoxycycloalkene carboxylates Vincent Tran and Thomas G. Minehan * Department of Chemistry and
More informationSupporting information
Supporting information Access to Aminated Saturated Oxygen Heterocycles via Copper-Catalyzed Aminooxygenation of Alkenes Jian Xie, Yue-Wei Wang, Lian-Wen Qi,* and Bo Zhang* State Key Laboratory of Natural
More informationSupporting Information for
Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 Supporting Information for
More informationDivergent Synthesis of CF 3 -Substituted Polycyclic Skeletons Based on Control of Activation Site of Acid Catalysts
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Divergent Synthesis of CF 3 -Substituted Polycyclic Skeletons Based on Control of Activation Site
More informationElectronic Supplementary Material (ESI) for Chemical Communications This journal is The Royal Society of Chemistry 2012
Ring Expansion of Alkynyl Cyclopropanes to Highly substituted Cyclobutenes via a N-Sulfonyl-1,2,3-Triazole Intermediate Renhe Liu, Min Zhang, Gabrielle Winston-Mcerson, and Weiping Tang* School of armacy,
More informationSupplementary Table S1: Response evaluation of FDA- approved drugs
SUPPLEMENTARY DATA, FIGURES AND TABLE BIOLOGICAL DATA Spheroids MARY-X size distribution, morphology and drug screening data Supplementary Figure S1: Spheroids MARY-X size distribution. Spheroid size was
More informationTotal Synthesis of (±)-Vibsanin E. Brett D. Schwartz, Justin R. Denton, Huw M. L. Davies and Craig. M. Williams. Supporting Information
Total Synthesis of (±)-Vibsanin E. Brett D. Schwartz, Justin R. Denton, Huw M. L. Davies and Craig M. Williams Supporting Information General Methods S-2 Experimental S-2 1 H and 13 C NMR Spectra S-7 Comparison:
More informationPoly(4-vinylimidazolium)s: A Highly Recyclable Organocatalyst Precursor for. Benzoin Condensation Reaction
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 24 Supporting Information Poly(4-vinylimidazolium)s: A Highly Recyclable rganocatalyst Precursor
More informationSupporting Information
Supporting Information Cobalt(II)-Catalyzed Acyloxylation of C- Bonds in Aromatic Amides with Carboxylic Acids Rina Ueno, Satoko atsui, and aoto Chatani* Department of Applied Chemistry, Faculty of Engineering,
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 214 Supporting Information Rapid and sensitive detection of acrylic acid using a novel fluorescence
More informationPhotooxidations of 2-(γ,ε-dihydroxyalkyl) furans in Water: Synthesis of DE-Bicycles of the Pectenotoxins
S1 Photooxidations of 2-(γ,ε-dihydroxyalkyl) furans in Water: Synthesis of DE-Bicycles of the Pectenotoxins Antonia Kouridaki, Tamsyn Montagnon, Maria Tofi and Georgios Vassilikogiannakis* Department of
More informationBrønsted Base-Catalyzed Reductive Cyclization of Alkynyl. α-iminoesters through Auto-Tandem Catalysis
Supporting Information Brønsted Base-Catalyzed Reductive Cyclization of Alkynyl α-iminoesters through Auto-Tandem Catalysis Azusa Kondoh, b and Masahiro Terada* a a Department of Chemistry, Graduate School
More informationSupporting Text Synthesis of (2 S ,3 S )-2,3-bis(3-bromophenoxy)butane (3). Synthesis of (2 S ,3 S
Supporting Text Synthesis of (2S,3S)-2,3-bis(3-bromophenoxy)butane (3). Under N 2 atmosphere and at room temperature, a mixture of 3-bromophenol (0.746 g, 4.3 mmol) and Cs 2 C 3 (2.81 g, 8.6 mmol) in DMS
More informationSynthesis and Use of QCy7-derived Modular Probes for Detection and. Imaging of Biologically Relevant Analytes. Supplementary Methods
Synthesis and Use of QCy7-derived Modular Probes for Detection and Imaging of Biologically Relevant Analytes Supplementary Methods Orit Redy a, Einat Kisin-Finfer a, Shiran Ferber b Ronit Satchi-Fainaro
More informationSupporting Information
Meyer, Ferreira, and Stoltz: Diazoacetoacetic acid Supporting Information S1 2-Diazoacetoacetic Acid, an Efficient and Convenient Reagent for the Synthesis of Substituted -Diazo- -ketoesters Michael E.
More informationSynthetic Studies on Norissolide; Enantioselective Synthesis of the Norrisane Side Chain
rganic Lett. (Supporting Information) 1 Synthetic Studies on Norissolide; Enantioselective Synthesis of the Norrisane Side Chain Charles Kim, Richard Hoang and Emmanuel A. Theodorakis* Department of Chemistry
More informationN-Heterocyclic Carbene-Catalyzed Conjugate Additions of Alcohols
J. Am. Chem. Soc. Supporting Information page S1 N-Heterocyclic Carbene-Catalyzed Conjugate Additions of Alcohols Eric M. Phillips, Matthias Riedrich, and Karl A. Scheidt* Department of Chemistry, Center
More informationTuning Porosity and Activity of Microporous Polymer Network Organocatalysts by Co-Polymerisation
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Tuning Porosity and Activity of Microporous Polymer Network Organocatalysts
More informationA Total Synthesis of Paeoveitol
A Total Synthesis of Paeoveitol Lun Xu, Fengyi Liu, Li-Wen Xu, Ziwei Gao, Yu-Ming Zhao* Key Laboratory of Applied Surface and Colloid Chemistry of MOE & School of Chemistry and Chemical Engineering, Shaanxi
More informationSupplementary Material
10.1071/CH13324_AC CSIRO 2013 Australian Journal of Chemistry 2013, 66(12), 1570-1575 Supplementary Material A Mild and Convenient Synthesis of 1,2,3-Triiodoarenes via Consecutive Iodination/Diazotization/Iodination
More informationPd(II) Catalyzed C3-selective arylation of pyridine with (hetero)arenes SUPPORTING INFORMATION
Pd(II) Catalyzed C3-selective arylation of pyridine with (hetero)arenes Guo-Lin Gao,, Wujiong Xia, Pankaj Jain and Jin-Quan Yu *, Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey
More informationTransition-Metal-Free Esterification of Amides via Selective N C Cleavage under Mild Conditions. Supporting Information
Transition-Metal-Free Esterification of Amides via Selective N C Cleavage under Mild Conditions Guangchen Li, Peng Lei,, and Michal Szostak*, Department of Chemistry, Rutgers University, 73 Warren Street,
More informationHow to build and race a fast nanocar Synthesis Information
How to build and race a fast nanocar Synthesis Information Grant Simpson, Victor Garcia-Lopez, Phillip Petemeier, Leonhard Grill*, and James M. Tour*, Department of Physical Chemistry, University of Graz,
More informationSupplementary Information. Mapping the Transmission Function of Single-Molecule Junctions
upplementary Information Mapping the Transmission Function of ingle-molecule Junctions Brian Capozzi 1, Jonathan Z. Low 2, Jianlong Xia 3, Zhen-Fei Liu 4, Jeffrey B. Neaton 5,6, Luis M. Campos 2, Latha
More informationSupporting Information
Supporting Information SmI 2 -Mediated Carbon-Carbon Bond Fragmentation in α-aminomethyl Malonates Qiongfeng Xu,, Bin Cheng, $, Xinshan Ye,*, and Hongbin Zhai*,,,$ The State Key Laboratory of Natural and
More informationSupporting Information for: Direct Conversion of Haloarenes to Phenols under Mild, Transition-Metal-Free Conditions
Supporting Information for: Direct Conversion of Haloarenes to Phenols under Mild, Transition-Metal-Free Conditions Patrick S. Fier* and Kevin M. Maloney* S1 General experimental details All reactions
More informationDepartment of Chemistry and Biochemistry, California State University Northridge, Northridge, CA Experimental Procedures
Supporting Information Low Temperature n-butyllithium-induced [3,3]-Sigmatropic Rearrangement/Electrophile Trapping Reactions of Allyl-1,1- Dichlorovinyl Ethers. Synthesis of - - and -lactones. Aaron Christopher
More informationSUPPLEMENTARY INFORMATION
DOI: 10.1038/NCHEM.1989 Cooperative activation of cyclobutanones and olefins leads to bridged ring systems by a catalytic [4+2] coupling Haye Min Ko and Guangbin Dong* Department of chemistry and biochemistry,
More informationFormal Total Synthesis of Optically Active Ingenol via Ring-Closing Olefin Metathesis
Formal Total Synthesis of Optically Active Ingenol via Ring-Closing Olefin Metathesis Kazushi Watanabe, Yuto Suzuki, Kenta Aoki, Akira Sakakura, Kiyotake Suenaga, and Hideo Kigoshi* Department of Chemistry,
More informationCurtius-Like Rearrangement of Iron-Nitrenoid Complex and. Application in Biomimetic Synthesis of Bisindolylmethanes
Supporting Information Curtius-Like Rearrangement of Iron-itrenoid Complex and Application in Biomimetic Synthesis of Bisindolylmethanes Dashan Li,, Ting Wu,, Kangjiang Liang,, and Chengfeng Xia*,, State
More informationSupporting Information
J. Am. Chem. Soc. Supporting Information S 1 The First Suzuki Cross-Coupling of Aryltrimethylammonium Salts. Simon B. Blakey and David W. C. MacMillan* Division of Chemistry and Chemical Engineering, California
More informationSupporting Information
Supporting Information Co III -Carbene Radical Approach to Substituted 1H-Indenes Braja Gopal Das, Andrei Chirila, Moniek Tromp, Joost N.H. Reek, Bas de Bruin* Supramolecular and Homogeneous Catalysis,
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supporting Information Enantioselective Synthesis of Axially Chiral Vinyl arenes through Palladium-catalyzed
More informationHualong Ding, Songlin Bai, Ping Lu,* Yanguang Wang*
Supporting Information for Preparation of 2-Amino-3-arylindoles via Pd-Catalyzed Coupling between 3-Diazoindolin-2-imines and Arylboronic Acids as well as Their Extension to 3-Aryl-3-fluoroindolin-2-imines
More informationSupporting Information. Organocatalytic Synthesis of N-Phenylisoxazolidin-5-ones and a One-Pot Synthesis of -Amino Acid Esters
Supporting Information rganocatalytic Synthesis of N-Phenylisoxazolidin-5-ones and a ne-pot Synthesis of -Amino Acid Esters Jayasree Seayad, Pranab K. Patra, Yugen Zhang,* and Jackie Y. Ying* Institute
More informationSUPPORTING INFORMATION. Fathi Elwrfalli, Yannick J. Esvan, Craig M. Robertson and Christophe Aïssa
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 SUPPORTING INFORMATION S1 Fathi Elwrfalli, Yannick J. Esvan, Craig M. Robertson and Christophe
More informationSupporting Information
Supporting Information Enantioselective Synthesis of 3-Alkynyl-3-Hydroxyindolin-2-ones by Copper-Catalyzed Asymmetric Addition of Terminal Alkynes to Isatins Ning Xu, Da-Wei Gu, Jing Zi, Xin-Yan Wu, and
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supporting Information Rh 2 (Ac) 4 -Catalyzed 2,3-Migration of -rrocenecarboxyl -Diazocarbonyl
More informationSupporting Information
Supporting Information Design and Enantioselective Synthesis of β-vinyl Tryptamine Building Blocks for Construction of Privileged Chiral Indole Scaffolds Tao-Yan Lin, Hai-Hong Wu, Jian-Jun Feng*, and Junliang
More informationSupporting Information
Supporting Information Synthesis of 2-Benzazepines from Benzylamines and MBH Adducts Under Rhodium(III) Catalysis via C(sp 2 ) H Functionalization Ashok Kumar Pandey, a Sang Hoon Han, a Neeraj Kumar Mishra,
More informationSupporting Information
Supporting Information (Tetrahedron. Lett.) Cavitands with Inwardly and Outwardly Directed Functional Groups Mao Kanaura a, Kouhei Ito a, Michael P. Schramm b, Dariush Ajami c, and Tetsuo Iwasawa a * a
More informationPalladium-Catalyzed Oxidative Cyclization of Tertiary Enamines for Synthesis of 1,3,4-Trisubstituted Pyrroles and 1,3-Disubstituted Indoles
Supporting Information for Palladium-Catalyzed Oxidative Cyclization of Tertiary Enamines for Synthesis of 1,3,4-Trisubstituted Pyrroles and 1,3-Disubstituted Indoles Xiao-Li Lian, Zhi-Hui Ren, Yao-Yu
More informationSUPPLEMENTARY INFORMATION
doi:10.1038/nature12761 Materials and Methods General Unless otherwise noted, all reactions were carried out under an atmosphere of argon, and all reagents were purchased from commercial suppliers and
More informationSupporting Information:
Enantioselective Synthesis of (-)-Codeine and (-)-Morphine Barry M. Trost* and Weiping Tang Department of Chemistry, Stanford University, Stanford, CA 94305-5080 1. Aldehyde 7. Supporting Information:
More information