Ct. The product can not be conveniently converted to any known structure.Ct. The solution cannot

Ct. The product can not be conveniently converted to any known structure.
Ct. The solution cannot be conveniently converted to any identified structure.NIH-PA Caspase 9 Storage & Stability Author IL-15 MedChemExpress Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptTypical Procedure for the -Amination from the AldehydeA modification of reported procedure38 was utilized. Dibenzyl azodicarboxylate (90 , 1.29 g, 3.9 mmol) and proline (70 mg, 0.6 mmol) in MeCN (10 mL) have been cooled down to -3 . The aldehyde (1.02 g 3.0 mmol) was then added along with the mixture was stirred at -3 for two h. The reaction was progressively warmed to 20 inside ca. 1 h. The mixture was then cooled to 0 , treated with MeOH (3 mL) and NaBH4 (240 mg, 6.0 mmol) and was stirred for five min at 0 . The reaction was quenched by 1M KHSO4. The aqueous resolution was extracted with EtOAc 3 times. The combined organic layers were dried with MgSO4, and concentrated in vacuo. Purification on the residue by flash chromatography on silica gel, eluting with 15 EtOAchexanes gave the preferred alcohol as white foamy solid.J Org Chem. Author manuscript; offered 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 prepared as outlined by the standard -amination procedure catalysed by (R)-Proline. Purification by flash chromatography afforded anti-9 as a white foamy solid (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), 5.37 five.10 (m, 4H), 4.45 4.12 (m, 2H), three.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 (100 MHz, CDCl3) 159.1, 157.4, 135.6, 133.three, 133.2, 129.six, 129.8, 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 10.3 min (minor 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 prepared in accordance with the typical -amidation procedure catalysed by (S)-Proline. Purification by flash chromatography afforded syn-9 as a white foamy strong (1.63 g, 85 isolated yield). 1H NMR (400 MHz, CDCl3) 7.69 7.62 (m, J = 13.five, six.six Hz, 4H), 7.50 7.24 (m, 16H), 6.96 (s, 1H), 5.30 5.22 (m, 3H), 5.13 (dd, J = 12.1, 9.six Hz, 1H), 4.36 four.16 (m, 2H), 3.86 three.70 (m, 2H), three.59 3.44 (m, 2H), 1.80 (br, 1H), 1.11 1.08 (m, 9H), 0.93 0.90 (m, 3H); 13C NMR (one hundred MHz, CDCl3) 158.6, 158.two, 156.eight,J Org Chem. Author manuscript; available in PMC 2014 December 06.Khumsubdee et al.Page156.5, 135.9, 135.six, 135.5, 135.four, 133.0, 130.1, 129.9, 128.six, 128.5, 128.1, 127.9, 127.8, 68.three, 64.0, 63.two, 60.six, 35.five, 27.0, 19.2, 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 10.2 min (minor diastereomer), tr 14.three min (big diastereomer).NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptTypical Process for the Hydrogenolysis and Benzylation with the AlcoholTo Raney ickel ( 0.three g, prewashed with.