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 637371 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
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
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
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
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
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
Table 3: Additive screening S7
Table 4: Fluoride screening S8
Table 5: Catalyst and temperature screening S9
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
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 7.85 7.81 (m, 1H), 7.81 7.79 (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 -84.54 (dt, J = 34.8, 3.4 Hz), -85.12 (d, J = 34.6 Hz); 13 C NMR (101 MHz, CDCl3) δ 166.93, 154.84 (dd, J1 = 298.6 Hz, J2 = 286.8 Hz), 137.68 (dd, J = 6.6, J2 = 1.3 Hz), 133.94 (dd, J1 = 6.5, J2 = 4.7 Hz), 130.12, 127.89 (t, J = 1.7 Hz), 127.19, 127.09 (d, J = 1.4 Hz), 88.53 (dd, J = 24.7, 7.8 Hz), 52.04, 30.36, 23.12 (dd, J1 = 2.6, J2 = 1.7 Hz), 21.99 (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), 5.07 4.93 (m, 2H), 3.92 (s, 3H), 3.48 3.33 (m, 1H), 2.86 2.75 (m, 1H), 2.71 2.59 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3) δ -69.43 (d, J = 9.0 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 166.6, 139.3 (q, J = 2.0 Hz), 133.2, 130.1, 129.8, 129.2, S11
126.3 (q, J = 280.5 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] + : 259.0946, found: 259.0946. 4-(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), 5.43-5.62 (m, 1H), 4.91-5.07 (m, 2H), 3.26-3.57 (m, 1H), 2.74-2.96 (m, 1H), 2.47-2.71(m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -63.4 (d, J = 9.3Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 139.5 (q, J = 2.0 Hz), 132.7, 132.4, 129.9, 126.3 (q, J = 280.6 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] + : 226.0844, found: 226.0838. 1-(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), 5.46-5.64 (m, 1H), 4.90-5.10 (m, 2H), 3.32-3.52 (m, 1H), 2.73-2.93 (m, 1H), 2.46-2.71 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.7 (s, 3F), -69.6 (d, J = 8.0Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 138.3 (q, J = 1.9 Hz), 133.1, 130.3 (q, J = 32.5 Hz), 129.5, 126.3 (q, J = 280.3 Hz), 125.6 (q, J = 3.8 Hz), 124.0 (q, J = 272.0 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] + : 269.0765, found: 269.0758. 1-(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), 5.48-5.60 (m, 1H), 5.00 (dd, J1 = 16.4 Hz, J2 = 1.8 Hz, 2H), 3.34-3.47 (m, 1H), 2.76-2.87 (m, 1H), 2.62-2.71 (m, 1H), 2.61 (s, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.4 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 197.5, 139.5 (q, J = 1.8 Hz),137.0, 133.3, 129.4, 128.6, 126.3 (q, J = 281.2 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] + : 243.0997, found: 243.0994. 1-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), 7.67 7.58 (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), 5.06 4.97 (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 -68.41 (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 151.1, 132.8, 132.6, 129.4 (q, J = 1.5 Hz), 129.0, 128.6 (q, J = 2.2 Hz), 126.1 (q, J = 281.0 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] + : 268.0561, found: 268.0561. S12
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 7.95 7.90 (m, 1H), 7.56 7.53 (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), 5.05 4.91 (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 -68.43 (d, J = 9.2 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 167.8, 135.8 (q, J = 2.1 Hz), 133.7, 132.1, 131.3, 130.7, 128.6 (q, J = 1.5 Hz), 127.7, 126.8 (q, J = 282.3 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] + : 259.0946, found:259.0945. 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), 7.20-7.26 (m, 2H), 6.08 (s, 1H), 5.46 (s, 1H), 3.86-3.98 (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 -68.6 (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, 126.3 (q, J = 282.0 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] + :260.0898, found: 260,0893. 1-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), 7.67 7.56 (m, 2H), 7.48 (ddd, J = 8.6, 6.6, 2.2 Hz, 1H), 4.72 (hept, J = 1.5 Hz, 1H), 4.67 4.52 (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 -68.77 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 151.1, 139.8, 132.7, 129.5 (q, J = 1.1 Hz), 129.0, 128.5 (q, J = 2.0 Hz), 126.2 (q, J = 280.5 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] + : 260.0898, found: 260.0893. 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 7.95 7.90 (m, 1H), 7.56 7.53 (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), 5.05 4.91 (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 -68.43 (d, J = 9.2 Hz, 3F); 13 C NMR (101 MHz, CDCl3) δ 167.9, 140.8, 135.6 (q, J = 2.1 Hz), 131.9, 131.3, 130.7, 128.7 (q, J = 1.0 Hz), 127.7, 126.9 (q, J = 279.7 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] + : 273.1102, found:273.1105. S13
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 -69.51 (d, J = 9.0 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 166.6, 140.1, 139.4 (q, J = 2.0 Hz), 130.1, 129.7, 129.2, 126.5 (q, J = 280.2 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] + : 273.1102, found: 273.1103. 4-(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 -69.46 (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (101 MHz, CDCl3) δ 138.6 (q, J = 2.0 Hz),138.6, 131.3, 128.9, 125.2 (q, J = 279.2 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] + : 240.1000, found: 240.0990. 1-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 8.19-8.25 (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), 3.56-3.72 (m, 1H), 2.75-2.87 (m, 1H), 2.59-2.73 (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, 136.3 (q, J = 1.8 Hz), 135.3, 139.6, 126.3 (q, J = 282.3 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]+: 260.0898 found: 260.0904. 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), 7.57-7.69 (m, 2H), 7.37-7.54 (m, 1H), 6.12 (s, 1H), 5.41 (s, 1H), 4.58-4.75 (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 -68.4 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.4, 151.3, 135.2, 132.7, 129.3 (q, J = 1.0 Hz), 129.2, 128.7, 128.1 (q, J = 2.0 Hz), 126.0 (q, J = 280.9 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] + : 304.0797, found: 304.0786. S14
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), 7.28-7.45 (m, 3H), 7.10-7.25 (m, 4H), 5.13 (s, 1H), 4.87 (s, 1H), 3.31-3.52 (m, 2H), 2.92 (dd, J1 = 15.3 Hz, J2 = 12.3 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.0 (d, J = 8.7 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 143.3, 139.4 (q, J = 1.9 Hz), 139.2, 132.2, 129.9, 128.7, 128.1, 126.3 (q, J = 281.0 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] + : 302.1157, found: 302.1151. 4-(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), 7.12-7.25 (m, 4H), 6.95-7.03 (m, 2H), 5.09 (s, 1H), 4.87 (s, 1H), 3.29-3.51 (m, 2H), 2.92 (dd, J1 = 14.4 Hz, J2 = 11.2 Hz, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.0 (d, J = 8.9 Hz, 3F), -113.7 (s,1f) ppm; 13 C NMR (100 MHz, CDCl3): δ 163.8, 161.3, 142.3, 139.2 (q, J = 1.1 Hz), 135.3 (d, J = 3.3 Hz), 132.3, 129.9, 127.8 (d, J = 8.0 Hz),126.2 (q, J = 278.7 Hz), 118.3, 116.7, 115.6 (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] + : 320.1062, found: 320.1063. 4-(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), 7.39-7.41 (m, 2H), 7.32-7.36(m, 3H), 5.35 (s, 1H), 5.18 (s, 1H), 3.78-3.89 (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 - 69.0 (d, J = 8.8Hz, 3F) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.0 (d, J = 8.8Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 139.2 (q, J = 1.7Hz), 132.3, 131.5, 130.0, 128.7, 128.4, 126.3, 126.2 (q, J = 282.8 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] + : 326.1157, found: 326.1149. (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 7.83-7.85 (m, 1H), 7.62-7.67 (m, 2H), 7.45-7.49 (m, 1H), 7.18-7.28 (m, 5H), 6.36 (d, J = 15.8 Hz, 1H), 6.00 (dt, J1 = 15.8 Hz, J2 = 7.3 Hz, 1H), 4.41-4.51 (m, 1H), 2.99-3.06 (m, 1H), 2.78-2.86 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.1 (q, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.1, 136.7, 133.6, 132.8, 129.3 (q, J = 1.4 Hz), 129.1, 128.6 (q, J = 2.1 Hz), 128.5, 127.5, 126.2, 126.1 (q, J = 280.0 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] + : 322.1055, found: 322.1053. S15
(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, 0.088 mmol, Yield: 59%); 1 H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 8.8 Hz, 1H), 7.63-7.69 (m, 2H), 7.44-7.51 (m, 1H), 7.15-7.22 (m, 2H), 6.91-6.97 (m, 2H), 6.32 (d, J = 15.6 Hz, 1H), 5.91 (dt, J1 = 14.8 Hz, J2 = 7.0 Hz, 1H), 4.35-4.50 (m, 1H), 2.93-3.07 (m, 1H), 2.72-2.85 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ-68.0 (d, J = 9.0 Hz, 3F), -114.5 (m, 1F) ppm; 13 C NMR (100 MHz, CDCl3): δ 163.5, 161.1, 151.1, 132.8, 132.5, 129.3 (q, J = 1.6 Hz), 129.1, 128.6 (q, J = 1.8 Hz), 127.7, 127.6, 126.4 (q, J = 282.5 Hz), 124.8, 123.8 (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] + : 340.0961 found: 340.0966. (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), 7.24-7.29 (m, 2H), 7.17-7.22 (m, 3H), 6.37 (d, J = 14.7 Hz, 1H), 5.88 (dt, J1 =14.1 Hz, J2 = 7.7 Hz, 1H), 3.39-3.58 (m, 1H), 2.91-3.07 (m, 1H), 2.72-2.97 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.2 (d, J = 8.7 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 139.6 (q, J = 2.0 Hz), 136.5, 133.7, 132.5, 129.9, 128.6, 127.7, 126.1, 125.8 (q, J = 286.6 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] + : 324.0976, found: 324.0981. (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, 0.084 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), 3.45-3.56 (m, 1H), 2.93-3.02 (m, 1H), 2.76-2.89 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.6 (s, 3F), -69.3 (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 166.5, 140.1, 139.1 (q, J = 1.7 Hz), 132.1, 130.3, 130.0 (q, J = 32.0 Hz), 130.0, 129.1,127.5, 126.3, 126.3 (q, J = 281.5 Hz), 125.5(q, J = 3.9 Hz), 124.1 (q, J = 273.1 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] + : 403.1133 found: 403.1118. (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
(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), 3.42-3.58 (m, 1H),2.93-3.01 (m, 1H), 2.73-2.88(m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.6 (s, 3F), -69.2 (d, J = 8.5 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 139.9 (q, J = 1.9 Hz), 139.4 (q, J = 1.9 Hz), 132.6, 132.5, 129.9, 129.6 (q, J = 32.6 Hz),126.9, 126.3, 126.0 (q, J = 280.3Hz), 125.5 (q, J = 3.9 Hz), 124.1 (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] + : 392.0850 found: 392.0854. (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), 7.53-7.60 (m, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.35-7.41 (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), 5.02-5.14 (m, 1H), 3.87 (s, 3H), 2.94-3.04 (m, 1H), 2.75-2.86 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.5 (s, 3F), -68.0 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 167.8, 140.5 (q, J = 1.6 Hz), 135.7 (q, J = 2.7 Hz), 132.2, 131.4, 131.2, 130.9, 129.1 (q, J = 32.5 Hz), 128.4 (q, J = 1.4 Hz), 128.3, 128.3 (q, J = 280.0 Hz), 127.9, 126.2, 125.4 (q, J = 3.5 Hz), 124.2 (q, J = 271.7 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] + : 403.1133 found: 403.1140. 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, 0.072 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), 7.43-7.53 (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), 4.39-4.53 (m, 1H), 3.89 (s, 3H), 2.99-3.10 (m, 1H), 2.76-2.90 (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, 129.2 (q, J = 1.8 Hz), 129.2, 129.1, 128.5 (q, J = 2.0 Hz), 126.9, 126.1, 126.0(q, J = 280.7 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] + : 380.1110 found: 380.1115. (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), 5.99-6.19 (m, 1H), 4.33-4.57 (m, 1H), 2.96-3.18 (m, 1H), 2.71-2.92 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.6 (s, 3F), -67.9 (d, J = 8.8 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.0, 140.1 (q, J = 1.2 Hz), 132.9, 132.4, 130.1 (q, J = 32.0 Hz), 129.2, 129.2 (q, J = 1.4 Hz), 128.4 (q, J = 2.1 Hz), 126.9, 126.3, 126.0(q, J = 282.2 Hz), 125.5 (q, J = 3.7 Hz), S17
124.8, 124.2 (q, J = 272.2 Hz), 42.9 (q, J = 27.1 Hz), 33.1 (q, J = 2.1 Hz) ppm; HRMS (ESI, m/z): calculated for [M+H] + : 390.0929, found: 390.0929. (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), 7.66-7.67 (m, 2H), 7.48-7.55 (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), 4.39-4.49 (m, 1H), 3.03-3.09 (m, 1H), 2.80-2.89 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -67.9 (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, 129.1 (q, J = 1.5 Hz), 128.3, 128.3 (q, J = 2.0 Hz), 126.7, 126.0 (q, J = 280.3 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] + : 347.1001, found: 347.1001. (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), 7.57-7.70 (m, 2H), 7.39-7.50 (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), 4.39-4.55 (m, 1H), 3.78 (s, 3H), 2.97-3.12 (m, 1H), 2.74-2.89 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.1 (d, J = 8.9 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 156.5, 151.1, 132.8, 129.5 (q, J = 1.4 Hz), 129.0, 128.8 (q, J = 2.1 Hz), 128.6, 128.6, 126.8, 126.1 (q, J = 280.0 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] + : 352.1161, found: 352.1160. (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), 7.61-7.66 (m, 2H), 7.45-7.49 (m, 1H), 7.17 (t, J = 7.8 Hz, 1H), 6.82 (d, J = 7.7 Hz, 1H), 6.73-6.76 (m, 2H), 6.33 (d, J = 15.7 Hz, 1H), 5.99 (dt, J1 = 15.7, J2 = 7.2 Hz, 1H), 4.40-4.49 (m, 1H), 3.78 (s, 3H), 2.99-3.05 (m,1h), 2.77-2.85 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.1 (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, 129.3 (q, J = 1.4 Hz), 129.1, 128.6 (q, J = 2.0 Hz), 126.1 (q, J = 279.1 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] + : 352.1161, found: 352.1156. S18
(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), 7.79-7.81 (m, 2H), 7.71-7.73 (m, 2H), 7.66 (t, J = 7.5 Hz, 1H), 7.43-7.49 (m, 3H), 7.36-7.38 (m, 2H), 7.06 (d, J = 15.5 Hz, 1H), 6.00 (dt, J1 =15.5 Hz, J2 = 7.2 Hz, 1H), 4.50-4.59 (m, 1H), 3.10-3.17 (m, 1H), 2.90-2.98 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.0 (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, 129.4 (q, J = 2.4 Hz), 129.1, 128.7 (q, J = 2.1 Hz), 128.5, 127.9, 127.3, 126.4 (q, J = 279.1 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] + : 372.1211, found: 372.1205. (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 8.42-8.43 (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), 7.47-7.51 (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), 4.40-4.50 (m, 1H), 3.02-3.08 (m, 1H), 2.80-2.88 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.0 (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, 128.4 (q, J = 1.9 Hz), 126.7, 126.0 (q, J = 279.2 Hz), 124.8, 123.5 (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] + : 323.1007, found: 323.1014. (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 7.82-7.90 (m, 1H), 7.56-7.68 (m, 2H), 7.42-7.52 (m, 1H), 6.12-6.28 (m, 1H), 5.95-6.08 (m, 1H), 5.40-5.54 (m, 1H), 5.04-5.22 (m, 1H), 4.26-4.46 (m, 1H), 2.82-2.96 (m, 1H), 2.62-2.77(m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.3 (d, J = 9.1 Hz, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 151.0 (q, J = 1.9 Hz), 136.6, 136.2, 134.6, 132.8, 129.3 (q, J = 1.4 Hz), 129.0, 127.9, 126.3 (q, J = 284.6 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] + : 297.0718, found: 297.0706. (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 7.83 6.14 (dd, J1 = 8.2 Hz, J2 = 1.1 Hz, 2H), 7.56-7.65 (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), 4.21-4.35 (m, 1H), 271-2.82 (m, 1H), 2.45-2.59 (m, 1H), 1.69-1.83 (m, 1H), 1.51-1.66 (m, 4H), 1.41-1.49 (m, 1H), 1.00-1.23 (m, 3H), 0.78-0.93 (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ -68.1 (d, J = 9.4 Hz, 3F) ppm; 13 C NMR (100 S19
MHz, CDCl3): δ 151.3, 141.2, 132.6, 129.5 (q, J = 1.5 Hz), 129.0 (q, J = 2.0 Hz), 128.8, 126.2 (q, J = 280.7 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] + : 328.1524 found: 328.1525. (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 -62.6 (s, 3F), -74.4 (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.5, 144.7, 139.9 (q, J = 1.3 Hz), 133.8, 129.5 (q, J = 32.4 Hz), 129.1, 127.4 (q, J = 283.8 Hz),126.3, 125.5 (q, J = 3.9 Hz), 125.1, 124.1 (q, J = 272.1 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] + : 404.1085 found: 404.1067. 1-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), 5.30-5.47 (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 -74.7 (s,3f) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.4, 144.9, 130.8, 129.2 (q, J = 1.1 Hz), 127.5 (q, J = 283.5 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] + : 260.0898, found: 260.0891. 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), 5.29-5.49 (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, 128.2 (q, J =0.9 Hz), 127.9 (q, J = 283.4 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] + : 273.1102, found: 273.1101. 1-(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
2H), 5.57-5.82 (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), 1.99-2.26 (m, 2H), 0.89 (t, J = 7.4 Hz, 3H) ppm; 19 F NMR (376 MHz, CDCl3): δ -62.7 (s, 3F), -69.9 (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 141.5, 132.2, 129.7 (q, J = 32.7 Hz), 128.7 (q, J = 1.1 Hz), 127.9 (q, J = 285.1 Hz), 125.1 (q, J = 4.0 Hz), 123.9 (q, J = 271.4 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] + : 297.1078 found: 297.1070. 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 7.74-7.89 (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), 2.02-2.17 (m, 1H), 1.84-1.99 (m, 2H), 1.66-1.80 (m, 1H) ppm; 19 F NMR (376 MHz, CDCl3): δ -70.9 (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, 128.9 (q, J = 2.4 Hz), 128.3 (q, J = 284.0 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] + : 371.1470, found: 371.1463. 1-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), 4.16-4.25 (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 -73.2 (s,3f) ppm; 13 C NMR (100 MHz, CDCl3): δ 168.9 (q, J = 1.3Hz), 167.1, 134.9, 129.7, 126.1 (q, J = 281.9 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] + : 269.1001, found: 269.0998. 1-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 7.34-7.38 (m, 3H), 7.29-7.34 (m, 2H), 6.19 (d, J = 1.1 Hz, 1H), 5.47 (d, J = 1.1 Hz, 1H), 4.29-4.39 (m, 1H), 4.18-4.28 (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 -67.1 (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 138.3 (q, J = 1.3 Hz), 137.4, 135.4, 134.2, 129.2, 128.4, 128.3, 128.0, 125.3 (q, J = 282.5 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] + :331.1157, found: 331.1155. S21
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 7.51-7.64 (m, 2H), 7.32-7.45 (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 -65.2 (s, 6F) ppm; 13 C NMR (100 MHz, CDCl3): δ 167.2, 133.3, 130.1, 129.2, 129.0, 128.9-129.0 (m), 128.5, 124.5 (q, J = 284.6 Hz), 58.6-59.6 (m), 52.1, 29.9-30.0 (m) ppm; HRMS (ESI, m/z): calculated for [M+H] + : 327.0820, found: 327.0814. 1-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), 5.52-5.75 (m, 2H), 5.01-5.29 (m, 4H), 2.93 (m, 2H), 2.80 (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.7 (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 147.2, 144.4, 131.3, 129.5 (q, J = 1.5 Hz), 127.3 (q, J = 285.6 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] + :286.1055, found: 286.1054. 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), 3.01-3.15 (m, 2H), 2.91-3.00 (m, 2H) ppm; 19 F NMR (376 MHz, CDCl3): δ -69.5 (s, 3F) ppm; 13 C NMR (100 MHz, CDCl3): δ 159.3, 147.3, 144.6, 134.3, 129.6, 129.6, 127.5 (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] + :498.1892, found: 498.1894. Reference [1] M. Hu, C. Ni, L. Li, Y. Han, J. Hu. J. Am. Chem. Soc. 2012, 134, 14496. [2] P. Tian, C. Feng, T.-P. Loh, Nat. commun. 2015, 6, 7472. S22
1H, 19F and 13C NMR spectra of structurally novel compounds S23
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