Ct. The solution can not be easily converted to any known structure.
Ct. The item can not be conveniently converted to any known structure.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptTypical Procedure for the -Amination from the AldehydeA modification of reported procedure38 was applied. Dibenzyl azodicarboxylate (90 , 1.29 g, 3.9 mmol) and proline (70 mg, 0.6 mmol) in MeCN (ten mL) were cooled down to -3 . The aldehyde (1.02 g 3.0 mmol) was then added plus the mixture was stirred at -3 for 2 h. The reaction was steadily warmed to 20 inside ca. 1 h. The mixture was then cooled to 0 , treated with MeOH (three mL) and NaBH4 (240 mg, six.0 mmol) and was stirred for 5 min at 0 . The reaction was quenched by 1M KHSO4. The aqueous answer was extracted with EtOAc three times. The combined organic layers were dried with MgSO4, and concentrated in vacuo. Purification from the residue by flash chromatography on silica gel, eluting with 15 EtOAchexanes gave the preferred alcohol as white foamy strong.J Org Chem. Author manuscript; readily ALK5 MedChemExpress available in PMC 2014 December 06.Khumsubdee et al.PageNIH-PA Author ManuscriptDibenzyl 1-((2R,3S)-4-((tert-Butyldiphenylsilyl)oxy)-1-hydroxy-3-methylbutan-2yl)hydrazine-1,2-dicarboxylate (anti-9) The compound was ready according to the typical -amination procedure catalysed by (R)-Proline. Purification by flash chromatography afforded anti-9 as a white foamy strong (1.54 g, 80 isolated yield). 1H NMR (400 MHz, CDCl3) 7.70 7.67 (m, 4H), 7.50 7.27 (m, 16H), six.85 (d, J = 31.1 Hz, 1H), five.37 five.ten (m, 4H), four.45 four.12 (m, 2H), 3.80 3.41 (m, 4H), 1.95 1.66 (m, 1H), 1.12 1.09 (m, 9H), 0.99 0.88 (m, 3H); 13C NMR (one hundred MHz, CDCl3) 159.1, 157.4, 135.6, 133.three, 133.2, 129.6, 129.eight, 128.7, 128.6, 128.two, 127.9, 127.8, 127.7, 68.62, 65.88, 65.56, 60.37, 35.6, 26.9, 19.three, 15.1. IR (CH2Cl2) n (cm-1) 3356, 3032, 2928, 1717, 1454, 1408, 1265, 1227, 1111, 1057. HRMS (ESI, TOF): mz = 641.3078, calcd For C37H45N2O6Si [MH] 641.3047. The diastereoselectivity was 1.0:13, determined by Chiral HPLC (Chiralcel OD, HexiPrOH 93:7, 1 mLmin, 25 ), tr 10.three min (minor CLK Compound diastereomer), tr 14.four min (important diastereomer).NIH-PA Author Manuscript NIH-PA Author ManuscriptDibenzyl 1-((2S,3S)-4-((tert-Butyldiphenylsilyl)oxy)-1-hydroxy-3-methylbutan-2yl)hydrazine-1,2-dicarboxylate (syn-9) The compound was ready based on the standard -amidation procedure catalysed by (S)-Proline. Purification by flash chromatography afforded syn-9 as a white foamy solid (1.63 g, 85 isolated yield). 1H NMR (400 MHz, CDCl3) 7.69 7.62 (m, J = 13.five, 6.six Hz, 4H), 7.50 7.24 (m, 16H), six.96 (s, 1H), 5.30 five.22 (m, 3H), 5.13 (dd, J = 12.1, 9.six Hz, 1H), four.36 4.16 (m, 2H), 3.86 three.70 (m, 2H), 3.59 3.44 (m, 2H), 1.80 (br, 1H), 1.11 1.08 (m, 9H), 0.93 0.90 (m, 3H); 13C NMR (100 MHz, CDCl3) 158.6, 158.two, 156.eight,J Org Chem. Author manuscript; out there in PMC 2014 December 06.Khumsubdee et al.Page156.five, 135.9, 135.6, 135.5, 135.four, 133.0, 130.1, 129.9, 128.six, 128.5, 128.1, 127.9, 127.eight, 68.three, 64.0, 63.two, 60.six, 35.5, 27.0, 19.two, 14.9. IR (CH2Cl2) n (cm-1) 3356, 3032, 2959, 1724, 1470, 1408, 1261, 1223, 1111, 1053. HRMS (ESI, TOF): mz = 641.3063 calcd For C37H45N2O6Si [MH] 641.3047. The diastereoselectivity was 62:1.0, determined by Chiral HPLC (Chiralcel OD, HexiPrOH 93:7, 1 mLmin, 25 ), tr 10.two min (minor diastereomer), tr 14.3 min (significant diastereomer).NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptTypical Process for the Hydrogenolysis and Benzylation of your AlcoholTo Raney ickel ( 0.3 g, prewashed with.