Supporting Information
|
|
- Madeleine Lamb
- 5 years ago
- Views:
Transcription
1 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 and Bioscience, Faculty of Science, Kagoshima University Korimoto, Kagoshima , Japan okam@sci.kagoshima-u.ac.jp Table of Contents General methods... S2 N-nosyl-3-hydroxy-2-pyridone (3b)... S2 Diels-Alder reaction of N-Ns- and N-Ts-pyridone 3b and 3c with acrylate ester... S3 Ethyl N-(2 -nitrobenzenesulfonyl)-2-aza-4-hydroxy-3-oxo-bicyclo[2.2.2]oct-5-ene-8-carboxylate (4b)... S3 Ethyl 2-hydroxy-2-hydroxymethyl-5-(2 -nitrobenzensulfonamido)-3-enecarboxylate (5b)... S4 Ethyl 5-(2 -nitrobenzenesulfonyl)-2-oxocyclohex-3-enylcarboxylate (6b) and its enol tautomer (6b)... S4 The equivalent of Corey s intermediate (2b)... S4 Ethyl 5-(tert-butoxycarbamoyl)-2-hydroxy-2-(hydroxymethyl)cyclohex-3-enecarboxylate (5b)... S5 Corey s intermediate (2a)... S5 1H NMR of 3b... S6 13C NMR of 3b... S7 1H NMR of 4b... S8 13C NMR of 4b... S9 1H NMR of 5b...S10 13C NMR of 5b... S11 1H NMR of 2b...S12 13C NMR of 2b...S13 1H NMR of 5a...S14 13C NMR of 5a...S15 1H NMR of 2a...S16 13C NMR of 2a...S17 S1
2 General methods Except the preparation of 3b that has been carried out under N 2 atmosphere, all reactions were performed directly in the air atmosphere. THF was distilled from Na-benzophenone. CH 3 CN and Me were also distilled before use. All the other chemicals were used as commercially available forms. Thin-layer chromatography (TLC) was performed using silica gel 60 F 254 precoated plates (Merck, thickness, 0.25 mm). Column chromatography was performed using silica gel 60 (Wako gel, mesh). NMR spectra were recorded on JEL FX-400 instrument in CDCl 3 or DMS using TMS as an internal reference. IR spectra were recorded on JASC FT/IR ESI-TFMS measurements were performed on a Bruker Daltonics micro TF-KS1focus. Typical procedures Ns N N-nosyl-3-hydroxy-2-pyridone (3b) The compound 3b was prepared by a modified procedure reported by Posner for the preparation of N-Ts-3-hydroxy-2-pyridone. 1 3b A solution of 3-(tert-butyldimethylsilyloxy)-2-pyridone (318 mg, 1.4 mmol) in THF (16 ml) was prepared under N 2 atmosphere at 0 ºC, and n-buli (1.6 N in hexane, 0.90 ml) was then added carefully and stirred for 20 min at the temperature. While stirring, 2-nitrobenzensulfonyl chloride (NsCl, 315 mg) was added and the temperature maintained at 0 ºC. After 24 h, the solution was warmed to room temperature and distilled water (15 ml) was added. The mixture was extracted with EtAc (3 x 10 ml) and the organic layer was dried over MgS 4. The solvent was removed under vacuo and the residue was purified by silica gel column chromatography using hexane-acet (4:1) to give a light yellow powder of 3-tert-butyldimethylsilyloxy-1-(2 -nitorobenzensulfonyl)-2-pyridone (515 mg, 89%). To the solution of the resulting product (526 mg, 1.3 mmol) in aqueous CH 3 C (1:1 mixture, 10.5 ml), two drops of conc. H 2 S 4 were added and the mixture was stirred for 30 h at room temperature. After the addition of water (1 ml), almost pure product 3b was obtained as a crystalline product by simple filtration (307 mg, 81%). M. p C; Elemental anal.: calcd for C 11 H 8 N 2 6 S: C, 44.60; N, 9.46; H, 2.72, found: C, 44.54; N, 9.27; H, 2.86; ESI-TFMS: m/z [M-H] - calcd for C 11 H 9 N 2 6 S: , found ; IR (KBr): 3322, 3125, 2363, 1658, 1624, 1534, 1390, 1350, 904, 858, 743, 652; 1 H NMR (400 MHz, DMS) 9.93 (1H, s), 8.44 (1H, dd, J = 7.6, 2.1 Hz), 8.09 (1H, dd, J = 8.1, 1.6), (2H, m), 7.40 (1H, dd, J = 7.8, 1.4), 6.79 (1H, dd, J = 7.3, 1.8 Hz), 6.36 (1H, t, J = 7.3); 13 C NMR (100 MHz, DMS) 156.3, 147.6, 147.5, 137.1, 135.0, 132.8, 128.7, 125.4, 121.3, 116.8, (1) Posner, H. G.; Vinader, V.; Afarinkia, K. J. rg. Chem. 1992, 57, S2
3 Diels-Alder reaction of N-Ns- and N-Ts-pyridone 3b and 3c with acrylate ester N-Nosyl protected pyridone 3b showed very different reactivity from N-tosyl pyridone 3c that was used for preparation of the starting material of validamine. 2 Compound 3c smoothly reacted with acrylate in CH 2 Cl 2 using Et 3 N as a catalyst (Table 1, entry 1). Under the same condition however, 3b gave only 3-hydroxy-2-(2 -nitrobenzensulfonyloxy)-pyridine and no desired DA adduct (entry 2). To prevent the Ns migration, several reaction conditions were examine, and finally a heterogeneous reaction of aqueous alkaline solution of 3b and excess ethyl acrylate was found to be an appropriate condition to give the corresponding DA adduct 4b in good yield without the migration (entry 3). Table 1. Base-Catalyzed DA reaction of 3 N-X 3b: X = Ns 3c: X = Ts + C 2 R base X N C2 R 4b: X = Ns 4c: X = Ts entry dienophile 1 R = Me, 1.1 eq. 2 R = Et, 1.1 eq. 3 R = Et, excess condition Et 3 N, CH 2 Cl 2, RT, 24 h Et 3 N, CH 2 Cl 2, RT, 24 h Na, H 2, RT, 24 h in suspension yeild (%) 66 a 0 b 83 a) ref. 2. b) N Ns was formed in 30 %. Ethyl N-(2 -nitrobenzenesulfonyl)-2-aza-4-hydroxy-3-oxo-bicyclo[2.2.2]oct-5-ene-8- Ns N carboxylate (4b) To a suspension of compound 3b (325 mg, 1.1 mmol) in water (12 ml), aqueous Na solution (2N, 1.1 ml) and ethyl acrylate (4.5 ml) were successively added, and the resulting 4b mixture was stirred vigorously at room temperature. After 24 h, the reaction mixture was extracted by CH 2 Cl 2 (3 x 10 ml) and the combined organic layer was dried over MgS 4 and concentrated under vaccuo to give crude crystalline product. Recrystallization in ether provided pure 4b as a single isomer (361 mg, 83% yield). M. p C; Elemental Anal.: calcd for C 16 H 16 N 2 8 S: C, 48.48; N, 7.07; H, 4.07, found: C, 48.49; N, 7.05; H, 4.14; ESI-TFMS: m/z [M-H] - calcd for C 16 H 16 N 2 8 S: , found ; IR (KBr): 3315, 3102, 2899, 1746, 1717, 1591, 1365, 1304, 960, 881; 1 H NMR (400 MHz, CDCl 3 ) 8.50 (1H, m), (2) kamura, H.; Nagaike, H.; Kipassa, N. T.; Iwagawa, T.; Nakatani, M. Heterocycles 2006, 68, S3
4 (3H, m), 6.70 (1H, t, J = 6.6 Hz), 6.26 (1H, dd, J = 8.0, 1.1 Hz), 5.53 (1H, m), 4.19 (2H, q, J = 7.3 Hz), 3.90 (1H, s), 2.93 (1H, dd, J = 9.6, 5.0 Hz), 2.69 (1H, m), 1.99 (1H, dd, J = 13.3, 5.0 Hz), 1.71 (1H, s), 1.25 (3H, t, J = 7.3 Hz); 13 C NMR (100 MHz, CDCl 3 ) 171.4, 171.3, 147.8, 135.3, 134.2, 134.0, 132.4, 131.6, 131.4, 124.6, 77.9, 61.6, 53.6, 43.2, 33.4, NHNs Ethyl 2-hydroxy-2-hydroxymethyl-5-(2 -nitrobenzensulfonamido)-3-enecarboxylate (5b) To a solution of 4b (294 mg, 0.74 mmol) in THF (8.0 ml), NaBH 4 (42 mg, 1.1 mmol) was added at 0 ºC. After stirring for two hours, the reaction was quenched by some drops of H 3 P 4 solutiojn (5%). The whole mixture was extracted with EtAc (3 x 5 ml) and the resulting organic layer was washed with brine and dried over Mg S 4. The solvent was 5b removed under vaccuo and the obtained residue was purified by silica gel column chromatography with Me-CH 2 Cl 2 (1:50) to afford the diol 5b as a pale yellow oil (229 mg, 77% yield). ESI-TFMS: m/z [M-H] - calcd for C 16 H 20 N 2 8 S , found ; IR (film): 3466, 2982, 2361, 1715, 1593, 1539, 1343, 855; 1 H NMR (400 MHz, CDCl 3 ) 8.17 (1H, m), 7.89 (1H, dd, J = 6.0, 3.2 Hz), (2H, m), 5.79 (1H, dd, J = 10.1, 1.4 Hz), 5.65 (1H, dd, J = 10.1, 4.6 Hz), 5.54 (1H, d, J = 7.8 Hz), 4.38 (1H, s), (3H, m), (2H, m), 2.96 (1H, dd, J = 10.3, 3.4 Hz), 2.36 (1H, br s), 2.29 (1H, m), 1.99 (1H, dt, J = 14.2, 4.1 Hz), 1.74 (2H, s), 1.25 (3H, t, J = 7.1 Hz); 13 C NMR (100 MHz, CDCl 3 ) 174.8, 147.8, 134.6, 133.7, 133.7, 133.0, 130.8, 128.5, 125.5, 70.3, 68.0, 61.4, 48.4, 41.2, 29.7, Ethyl 5-(2 -nitrobenzenesulfonyl)-2-oxocyclohex-3-enylcarboxylate NHNs NHNs (6b) and its enol tautomer (6b) To a solution of diol 5b (205 mg, 0.51 mmol) in THF:H 2 (1:1, 8.0 ml), NaI 4 (163.6 mg) was added at 0 ºC. The solution was stirred for 6b three hours at the temperature, warmed to room temperature and then 6b' diluted by addition of water (5 ml). The resulting clear solution was extracted with ethyl acetate (3 x 5 ml). The combined organic layer was washed with brine and dried over anhydrous MgS 4, then filtered and concentrated. The residue was purified by silica gel chromatography with Hexane:EtAc (7:3) to afford the desired product as nearly 1:1 mixture of the enone 6b and its enol tautomer 6b (151 mg, 80% yield). Since the resulting mixture was relatively unstabele, it was used for next step without detailed spectra examinations. NHNs The equivalent of Corey s intermediate (2b) The mixture of 6b and 6b (160 mg, 0.44 mmol) and cerium trichloride (148 mg) were dissolved in Me (4.0 ml) at 0 ºC and NaBH 4 (27 mg) was added. The reaction mixture was 2b stirred at this temperature for 2 h, and then quenched by adding saturated aqueous solution of NH 4 Cl (ca. 1 ml). After removing Me under reduced pressure, the residue was diluted in water (ca. 5 ml) and extracted with ethyl acetate (3 x 10 ml). The organic layer was washed with brine, dried over MgS 4, filtered through celite, and concentrated. The resulting syrup containing corresponding alcohol was dissolved in THF (9.0 ml) with Et 3 N (290 µl) and DMAP (80 mg). The solution was cooled to 0 ºC, and then MsCl (112 mg) was added. The resulting white suspension was left to slowly warm to S4
5 room temperature while stirring for 4 h. After adding water (ca. 5 ml), the whole mixture was extracted with AcEt (3 x 10 ml). The combined organic layer was dried over MgS 4, filtered and concentrated. The resulting crude product was purified by silica gel column chromatography with hexane-acet (7:3) to yield the desired product 2b as a pale yellow oil (87 mg, 76% yield over two steps). ESI-TFMS: m/z [M-H] - calcd for C 15 H 16 N 2 6 S: , found ; IR (film): 3297, 3098, 2984, 1701, 1642, 1578, 1537, 1346, 1165, 1100, 854; 1 H NMR (400 MHz, CDCl 3 ) 8.20 (1H, m), 7.89 (1H, m), (2H, m), 6.21 (1H, dd, J = 9.4, 5.7), 6.00 (1H, dd, J = 9.6, 5.0), 5.53 (1H, d, J = 9.2), 4.31 (1H, m), 4.16 (2H, q, J = 6.9 Hz), 2.75 (1H, dd, J = 18.1, 5.8), 2.51 (1H, ddd, J = 18.1, 8.0, 2.5), 1.26 (3H, t, J = 7.1); 13 C NMR (100 MHz, CDCl 3 ) 166.1, 147.7, 135.2, 133.7, 133.2, 131.5, 130.6, 130.3, 126.7, 126.3, 125.6, 125.5, 60.7, 47.5, 28.6, NHBoc Ethyl 5-(tert-butoxycarbamoyl)-2-hydroxy-2-(hydroxymethyl)cyclohex-3-enecarboxylate (5a) To a solution of the 5b (338 mg, 0.85 mmol) in MeCN (4.0 ml) was added K 2 C 3 (152 mg) and PhSH (130 µl), and the resulting reaction mixture was stirred for 3 h at room temperature. The solution was diluted with water (10 ml) and washed with AcEt (2 x 5 ml). 5a To the aqueous layer, Boc 2 (204 mg) was added. The mixture was stirred for 24 h and extracted with AcEt (3 8 ml). The combined organic layer were dried over MgS 4 and concentrated in vacuo. The residue was purified by silica gel column chromatography with hexane-acet (4:1) to give 5a as a colorless oil (124 mg, 55% yield). ESI-TFMS: m/z [M+Na] + calcd for C 15 H 25 N 6 Na: , found: ; IR (film): 3362, 2978, 2936, 1689, 1522, 1456, 1393, 1248, 1171, 995, 779; 1 H NMR (400 MHz, CDCl 3 ) 5.84 (1H, dd, J = 10.1, 3.7 Hz), 5.76 (1H, dd, J = 10.1, 1.4 Hz), 4.57 (1H, br s), 4.46 (1H, s), 4.26 (1H, br s), 4.21 (2H, q, J = 7.3 Hz), (2H, m), 2.91 (1H, dd, J = 9.6, 2.7 Hz), (2H, m), 1.91 (1H, dt, J = 13.3, 4.1 Hz), 1.70 (2H, s), 1.45 (9H, s), 1.30 (3H, t, J = 7.1 Hz); 13 C NMR (100 MHz, CDCl 3 ) 175.3, 155.0, 132.2, 130.5, 108.7, 70.5, 68.2, 61.4, 41.7, 29.4, 28.4, NHBoc Corey s intermediate (2a) The experimental procedures for the conversions from 5a to 2a were essentially same with the above mentioned method. The spectra data of 2a showed good agreement with that of reported values. 3 ESI-TFMS: m/z [M+Na] + calcd for C 14 H 21 N 4 Na: , found 2a ; IR (film): 3353, 2978, 2361, 1707, 1512, 1368, 1254, 1167, 1098, 478, 444; 1 H (400 MHz, CDCl 3 ): 7.06 (1H, d, J = 4.1 Hz), (2H, m), 4.64 (1H, br s), 4.44 (1H, br s), 4.22 (2H, q, J = 7.1), (2H, m), 1.40 (9H, s), 1.31 (3H, t, J = 7.1 Hz); 13 C (100 MHz, CDCl 3 ): 166.9, 154.9, 132.5, 131.8, 128.9, 127.0, 124.8, 60.6, 53.4, 28.9, 28.4, (3) Yeung, Y.-Y.; Hong, S.; Corey, E. J. J. Am. Chem. Soc. 2006, 128, S5
6 1 H NMR of 3b N 3b Ns S6
7 13 C NMR of 3b N 3b Ns S7
8 1 H NMR of 4b Ns N 4b S8
9 13 C NMR of 4b Ns N 4b S9
10 1 H NMR of 5b NHNs 5b S10
11 13 C NMR of 5b NHNs 5b S11
12 1 H NMR of 2b NHNs 2b S12
13 13 C NMR of 2b NHNs 2b S13
14 1 H NMR of 5a NHBoc 5a S14
15 13 C NMR of 5a NHBoc 5a S15
16 1 H NMR of 2a NHBoc 2a S16
17 13 C NMR of 2a NHBoc 2a S17
The 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 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
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 informationSupporting Information. Expeditious Construction of the DEF Ring System of Thiersinine B
Supporting Information Expeditious Construction of the DEF Ring System of Thiersinine B Masaru Enomoto and Shigefumi Kuwahara* Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural
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 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 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 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 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 informationSupporting Information
Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany Diphenylprolinol Silyl Ether in Enantioselective, Catalytic Tandem Michael-Henry Reaction for the Control of Four Stereocenters Yujiro Hayashi*,
More informationSynthesis 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 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 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 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 (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 informationSupporting Information
Supporting Information An L-proline Functionalized Metallo-organic Triangle as Size-Selective Homogeneous Catalyst for Asymmertry Catalyzing Aldol Reactions Xiao Wu, Cheng He, Xiang Wu, Siyi Qu and Chunying
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 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 informationEnantioselective Synthesis of Fused Heterocycles with Contiguous Stereogenic Centers by Chiral Phosphoric Acid-Catalyzed Symmetry Breaking
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Enantioselective Synthesis of Fused Heterocycles with Contiguous Stereogenic Centers by Chiral
More informationSupporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2002
Supporting Information for Angew. Chem. Int. Ed. Z50016 Wiley-VCH 2002 69451 Weinheim, Germany Total Synthesis of (±)-Wortmannin Takashi Mizutani, Shinobu Honzawa, Shin-ya Tosaki, and Masakatsu Shibasaki*
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
1 A regiodivergent synthesis of ring A C-prenyl flavones Alberto Minassi, Anna Giana, Abdellah Ech-Chahad and Giovanni Appendino* Dipartimento di Scienze Chimiche, Alimentari, Farmaceutiche e Farmacologiche
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 informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Concise Stereoselective Synthesis of ( )-Podophyllotoxin by Intermolecular Fe III -catalyzed Friedel-Crafts Alkylation Daniel Stadler, Thorsten
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
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 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 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 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 informationSupplementary Material for: Unexpected Decarbonylation during an Acid- Mediated Cyclization to Access the Carbocyclic Core of Zoanthenol.
Tetrahedron Letters 1 Pergamon TETRAHEDRN LETTERS Supplementary Material for: Unexpected Decarbonylation during an Acid- Mediated Cyclization to Access the Carbocyclic Core of Zoanthenol. Jennifer L. Stockdill,
More informationSUPPORTING INFORMATION
UPPRTING INFRMATIN Application of a Rhodium-Catalyzed Addition/Cyclization equence Toward the ynthesis of Polycyclic eteroaromatics Nai-Wen Tseng and Mark Lautens* Davenport Laboratories, Chemistry Department,
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 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 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 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 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 informationSupplementary Information. Novel Stereocontrolled Amidoglycosylation of Alcohols with Acetylated Glycals and Sulfamate Ester
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Supplementary Information Novel Stereocontrolled Amidoglycosylation of Alcohols with Acetylated
More informationEnhanced Radical-Scavenging Activity of Naturally-Oriented Artepillin C Derivatives
Supporting nformation Enhanced Radical-Scavenging Activity of Naturally-Oriented Artepillin C Derivatives Sushma Manda, a kuo Nakanishi,* a,b Kei Ohkubo, b Yoshihiro Uto, c Tomonori Kawashima, b Hitoshi
More informationFacile Synthesis of Flavonoid 7-O-Glycosides
Facile Synthesis of Flavonoid 7-O-Glycosides Ming Li, a Xiuwen Han, a Biao Yu b * a State Key Laboratory of Catalyst, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
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
Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany Total Synthesis of Cassialoin, Anthrone C-Glycoside Yasuhito Koyama, Ryo Yamaguchi and Keisuke Suzuki* Department of Chemistry, Tokyo Institute
More informationSupporting Information. (1S,8aS)-octahydroindolizidin-1-ol.
SI-1 Supporting Information Non-Racemic Bicyclic Lactam Lactones Via Regio- and cis-diastereocontrolled C H insertion. Asymmetric Synthesis of (8S,8aS)-octahydroindolizidin-8-ol and (1S,8aS)-octahydroindolizidin-1-ol.
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 informationSupplementary Information (Manuscript C005066K)
Supplementary Information (Manuscript C005066K) 1) Experimental procedures and spectroscopic data for compounds 6-12, 16-19 and 21-29 described in the paper are given in the supporting information. 2)
More informationEfficient Syntheses of the Keto-carotenoids Canthaxanthin, Astaxanthin, and Astacene
Efficient Syntheses of the Keto-carotenoids Canthaxanthin, Astaxanthin, and Astacene Seyoung Choi and Sangho Koo* Department of Chemistry, Myong Ji University, Yongin, Kyunggi-Do, 449-728, Korea. E-mail:
More informationSupplementary Information
Supplementary Information C aryl -C alkyl bond formation from Cu(ClO 4 ) 2 -mediated oxidative cross coupling reaction between arenes and alkyllithium reagents through structurally well-defined Ar-Cu(III)
More informationBulletin of the Chemical Society of Japan
Supporting Information Bulletin of the Chemical Society of Japan Enantioselective Copper-Catalyzed 1,4-Addition of Dialkylzincs to Enones Followed by Trapping with Allyl Iodide Derivatives Kenjiro Kawamura,
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 informationRecyclable Enamine Catalysts for Asymmetric Direct Cross-Aldol
Recyclable Enamine Catalysts for Asymmetric Direct Cross-Aldol Reaction of Aldehydes in Emulsion Media Qiang Gao, a,b Yan Liu, a Sheng-Mei Lu, a Jun Li a and Can Li* a a State Key Laboratory of Catalysis,
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 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 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 informationSupporting Information
Supporting Information Wiley-VCH 2012 69451 Weinheim, Germany Substitution of Two Fluorine Atoms in a Trifluoromethyl Group: Regioselective Synthesis of 3-Fluoropyrazoles** Kohei Fuchibe, Masaki Takahashi,
More informationMetal-free general procedure for oxidation of secondary amines to nitrones
S1 Supporting information Metal-free general procedure for oxidation of secondary amines to nitrones Carolina Gella, Èric Ferrer, Ramon Alibés, Félix Busqué,* Pedro de March, Marta Figueredo,* and Josep
More informationA Mild, Catalytic and Highly Selective Method for the Oxidation of α,β- Enones to 1,4-Enediones. Jin-Quan Yu, a and E. J.
A Mild, Catalytic and Highly Selective Method for the Oxidation of α,β- Enones to 1,4-Enediones Jin-Quan Yu, a and E. J. Corey b * a Department of Chemistry, Cambridge University, Cambridge CB2 1EW, United
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 informationAmelia A. Fuller, Bin Chen, Aaron R. Minter, and Anna K. Mapp
Supporting Information for: Concise Synthesis of b-amino Acids via Chiral Isoxazolines Amelia A. Fuller, Bin Chen, Aaron R. Minter, and Anna K. Mapp Experimental Section General. Unless otherwise noted,
More informationStraightforward Synthesis of Enantiopure (R)- and (S)-trifluoroalaninol
S1 Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2010 Straightforward Synthesis of Enantiopure (R)- and (S)-trifluoroalaninol Julien
More informationHai-Bin Yang, Xing Fan, Yin Wei,* Min Shi*
Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2015 Solvent-controlled Nucleophilic Trifloromethylthiolation of Morita- Baylis-Hillman
More informationSupporting Information: Regioselective esterification of vicinal diols on monosaccharide derivatives via
Supporting Information: Regioselective esterification of vicinal diols on monosaccharide derivatives via Mitsunobu reactions. Guijun Wang,*Jean Rene Ella-Menye, Michael St. Martin, Hao Yang, Kristopher
More informationSupporting Information
Supporting Information Total Synthesis and Structural Reassignment of (±)-Cereoanhydride Zhiqiang Ren, Yu Hao, Xiangdong Hu* Department of Chemistry & Material Science, Key Laboratory of Synthetic and
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 informationEnantioselectivity switch in copper-catalyzed conjugate addition. reaction under influence of a chiral N-heterocyclic carbene-silver complex
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supplementary Information Enantioselectivity switch in copper-catalyzed conjugate addition
More informationSimplified platensimycin analogues as antibacterial agents
Simplified platensimycin analogues as antibacterial agents Dragan Krsta, a Caron Ka, a Ian T. Crosby, a Ben Capuano a and David T. Manallack a * a Medicinal Chemistry and Drug Action, Monash Institute
More informationSupporting Information For:
Supporting Information For: Peptidic α-ketocarboxylic Acids and Sulfonamides as Inhibitors of Protein Tyrosine Phosphatases Yen Ting Chen, Jian Xie, and Christopher T. Seto* Department of Chemistry, Brown
More informationSupporting Information
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2012 Subcellular Localization and Activity of Gambogic Acid Gianni Guizzunti,* [b] Ayse Batova, [a] Oraphin Chantarasriwong,
More informationDiaza [1,4] Wittig-type rearrangement of N-allylic-N- Boc-hydrazines into -amino-n-boc-enamines
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2016 Diaza [1,4] Wittig-type rearrangement of N-allylic-N- Boc-hydrazines into -amino-n-boc-enamines
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 informationOpioid ligands with mixed properties from substituted enantiomeric N-phenethyl-5-
Supplementary Information for: Opioid ligands with mixed properties from substituted enantiomeric N-phenethyl-5- phenylmorphans. Synthesis of a μ-agonist δ antagonist and δ-inverse agonists Kejun Cheng,
More informationSupporting Information
Supporting Information Organocatalytic Enantioselective Formal Synthesis of Bromopyrrole Alkaloids via Aza-Michael Addition Su-Jeong Lee, Seok-Ho Youn and Chang-Woo Cho* Department of Chemistry, Kyungpook
More informationSupporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003
Supporting Information for Angew. Chem. Int. Ed. Z50567 Wiley-VCH 2003 69451 Weinheim, Germany Metallacarborane-Based Nanostructures: A Carbon-Wired Planar Octagon** Haijun Yao, Michal Sabat, and Russell
More informationSynthesis of fluorophosphonylated acyclic nucleotide analogues via Copper (I)- catalyzed Huisgen 1-3 dipolar cycloaddition
Synthesis of fluorophosphonylated acyclic nucleotide analogues via Copper (I)- catalyzed Huisgen 1-3 dipolar cycloaddition Sonia Amel Diab, Antje Hienzch, Cyril Lebargy, Stéphante Guillarme, Emmanuel fund
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 informationSupporting Information
Supporting Information Wiley-VCH 2011 69451 Weinheim, Germany Enantioselective Total Synthesis of ( )-Jiadifenolide** Jing Xu, Lynnie Trzoss, Weng K. Chang, and Emmanuel A. Theodorakis* anie_201100313_sm_miscellaneous_information.pdf
More informationSupporting Information for. Singlet oxygen initiated cascade transformation of a simple difuran into the key ABC motif of the pectenotoxins
Supporting Information for Singlet oxygen initiated cascade transformation of a simple difuran into the key ABC motif of the pectenotoxins Georgios Vassilikogiannakis, * Ioanna Alexopoulou, Maria Tofi
More informationSupporting information. *Corresponding Author: Telephone number: , Fax number: ; address:
Supporting information Synthesis of indolizidine, pyrrolizidine and quinolizidine ring systems by proline-catalyzed sequential -amination and HWE olefination of an aldehyde Shruti Vandana Kauloorkar, a
More informationSupplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry Supplementary data
Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2012 Supplementary data Cu-catalyzed in situ generation of thiol using xanthate as thiol
More informationHighly stereocontrolled synthesis of trans-enediynes via
Supporting Information for Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes Tsutomu Konno*, Misato Kishi, and Takashi Ishihara Address: Department of Chemistry
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 informationSupporting Information
ne-pot synthesis of pyrrolidino- and piperidinoquinolinones by three-component aza-diels Alder reactions of -arylimines with in situ generated cyclic enamides. Wenxue Zhang, Yisi Dai, Xuerui Wang, Wei
More informationSUPPORTING INFORMATION
SUPPRTING INFRMATIN A Direct, ne-step Synthesis of Condensed Heterocycles: A Palladium-Catalyzed Coupling Approach Farnaz Jafarpour and Mark Lautens* Davenport Chemical Research Laboratories, Chemistry
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 informationTable of Contents 1. General procedure for the chiral phosphoric acid catalyzed asymmetric reductive amination using benzothiazoline
Enantioselective Organocatalytic Reductive Amination of Aliphatic Ketones by Benzothiazoline as Hydrogen Donor Kodai Saito, Takahiko Akiyama* Department of Chemistry, Faculty of Science, Gakushuin University,
More informationPhil S. Baran*, Jeremy M. Richter and David W. Lin SUPPORTING INFORMATION
Direct Coupling of Pyrroles with Carbonyl Compounds: Short, Enantioselective Synthesis of (S)-Ketorolac Phil S. Baran*, Jeremy M. Richter and David W. Lin SUPPRTIG IFRMATI General Procedures. All reactions
More informationSupporting Information
Supporting Information Selective Synthesis of [6]-, [8]-, and [10]Cycloparaphenylenes Eiichi Kayahara, 1,2 Takahiro Iwamoto, 1 Toshiyasu Suzuki, 2,3 and Shigeru Yamago* 1,2 1 Institute for Chemical Research,
More informationSupporting Information
Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany SUPPRTIG MATERIAL Base Dependence in Copper-catalyzed Huisgen Reactions: Efficient Formation of Bistriazoles Yu Angell and Kevin Burgess *
More informationSupporting Information
Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany rganocatalytic Conjugate Addition of Malonates to a,ß-unsaturated Aldehydes: Asymmetric Formal Synthesis of (-)-Paroxetine, Chiral Lactams
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 informationSupporting Information for
Page of 0 0 0 0 Submitted to The Journal of Organic Chemistry S Supporting Information for Syntheses and Spectral Properties of Functionalized, Water-soluble BODIPY Derivatives Lingling Li, Junyan Han,
More informationSupplementary Information
Supplementary Information NE Difference Spectroscopy: SnPh 3 CH (b) Me (b) C()CH (a) Me (a) C()N Me (d) Me (c) Irradiated signal Enhanced signal(s) (%) Me (a) Me (c) 0.5, Me (d) 0.6 Me (b) - Me (c) H (a)
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 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. Table of Contents. 1. General Notes Experimental Details 3-12
Supporting Information Table of Contents page 1. General Notes 2 2. Experimental Details 3-12 3. NMR Support for Timing of Claisen/Diels-Alder/Claisen 13 4. 1 H and 13 C NMR 14-37 General Notes All reagents
More informationSupporting Information
Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany A Highly Enantioselective Brønsted Acid Catalyst for the Strecker Reaction Magnus Rueping, * Erli Sugiono and Cengiz Azap General: Unless otherwise
More informationDepartment of Chemistry, Colorado State University, Fort Collins, Colorado University of Colorado Cancer Center, Aurora, Colorado 80045
Improved Biomimetic Total Synthesis of d,l-stephacidin A Thomas J. Greshock 1 and Robert M. Williams 1,2 * 1 Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523 2 University
More informationA Meldrum s Acid-Derived Thione Dienophile in a Convergent and Stereoselective Synthesis of a Tetracyclic Quassinoid Intermediate
A ldrum s Acid-Derived Thione Dienophile in a Convergent and Stereoselective Synthesis of a Tetracyclic Quassinoid Intermediate Stéphane Perreault and Claude Spino* Supporting Information Experimental
More informationStereocontrolled Synthesis of Functionalized cis- Reactions of Azomethine Imines
Stereocontrolled Synthesis of Functionalized cis- Cyclopentapyrazolidines by 1,3-Dipolar Cycloaddition Reactions of Azomethine Imines Joshua Gergely, Jeremy B. Morgan, and Larry E. verman* Department of
More informationSupporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003
Supporting Information for Angew. Chem. Int. Ed. Z53001 Wiley-VCH 2003 69451 Weinheim, Germany 1 Ordered Self-Assembly and Electronic Behavior of C 60 -Anthrylphenylacetylene Hybrid ** Seok Ho Kang 1,
More information*Corresponding author. Tel.: , ; fax: ; Materials and Method 2. Preparation of GO nanosheets 3
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Synthesis of 2,3-dihydroquinazolinones and quinazolin-4(3h)-one catalyzed by Graphene Oxide
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 information