Luting with 2.5 5.0 EtOAc/hexanes gave the preferred alcohol as colorless oil.Standard Procedure for Preparation EpoxidesUnder Ar, to a answer of 7 (75.4 mg, 0.two mmol) in anhydrous THF was added NaH (ten.0 mg, 0.4 mmol) along with the mixture was stirred at 60 for 4 h. The reaction was quenched by 1 M KHSO4. The aqueous solution was extracted with CH2Cl2 3 occasions. The combined organic layers had been dried with MgSO4, and XIAP Antagonist MedChemExpress concentrated in vacuo. Purification on the residue by flash chromatography on silica gel, eluting with CH2Cl2/hexanes (20 ) gave the preferred epoxide as a colorless oil.Khumsubdee et al.Web page(2S,3R)-4-((tert-Butyldiphenylsilyl)oxy)-2-chloro-3-methylbutan-1-ol (syn-7) The compound was prepared based on the common -chlorination mTORC1 Activator Molecular Weight process catalysed by (S)-5-benzyl-2,2,3,-trimethylimidazolidin-4-one trifluoroacetic acid salt. Purification by flash chromatography afforded syn-7 as a colorless oil (147 mg, 78 isolated yield). 1H NMR (400 MHz, CDCl3) 7.81 7.75 (m, 4H), 7.54 7.44 (m, 6H), 4.49 four.45 (m, 1H), three.88 3.86 (m, 2H), three.71 3.62 (m, 2H), 2.34 (br, 1H), two.22 2.16 (m, 1H), 1.12 (s, 9H), 1.05 (d, J = 6.7 Hz, 3H); 13C NMR (one hundred MHz, CDCl3) 135.6, 135.six, 133.two, 129.eight, 127.8, 66.five, 65.7, 65.7, 38.8, 26.9, 19.3, 11.eight. IR (CH2Cl2) n (cm-1) 3356, 3071, 2932, 2859, 2361, 1470, 1427, 1377, 1111, 822. HRMS (ESI, TOF): m/z = 377.1718, calcd For C21H30ClO2Si [M+H]+ 377.1704. The diastereoselectivity was 18:1.0, determined by 1H NMR and confirmed by Chiral HPLC (Chiralcel OD, Hex/iPrOH 99:1, 1 mL/min, 25 ), tr 11.7 min (major diastereomer), tr 12.7 min (minor diastereomer). The product was converted towards the epoxide based on the common procedure for preparation epoxides. Purification by flash chromatography afforded (2R,3R)-4-tertbutyldiphenylsilyloxy-1,3-epoxy-3-methylbutane (anti-10) as a colorless oil (67.5 mg, 95 isolated yield). 1H NMR (400 MHz, CDCl3) 7.70 7.67 (m, 4H), 7.49 7.38 (m, 6H), three.66 (dd, J = 6.three, 1.6 Hz, 2H), two.90 two.87 (m, 1H), 2.79 (dd, J = four.9, 4.1 Hz, 1H), two.63 (dd, J = five.0, 2.8 Hz, 1H), 1.65 1.56 (m, 1H), 1.09 (s, 9H), 1.03 (d, J = six.8 Hz, 3H); 13C NMR (one hundred MHz, CDCl3) 135.6, 133.six, 129.7, 127.7, 66.4, 55.1, 46.8, 39.1, 26.8, 19.two, 13.3. IR (CH2Cl2) n (cm-1) 3070, 2927, 2859, 2338, 1462, 1427, 1389, 1362, 1111, 933.6, 887.3, 821.7. HRMS (ESI, TOF): m/z = 347.2020, calcd For C21H28O2SiLi [M+Li]+ 347.2019.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author Manuscript(2R,3R)-4-((tert-Butyldiphenylsilyl)oxy)-2-chloro-3-methylbutan-1-ol (anti-7) The compound was prepared in line with the standard chlorination process catalysed by (R)-5-benzyl-2,two,three,-trimethylimidazolidin-4-one trifluoroacetic acid salt. Purification by flash chromatography afforded anti-7 as colorless oil (141 mg, 75 isolated yield). 1H NMR (400 MHz, CDCl3) 7.74 7.68 (m, 4H), 7.51 7.39 (m, 6H), 4.26 four.22 (m, 1H), three.95 (dd, J = 12.2, four.five Hz, 1H), three.87 (dd, J = 12.two, six.five Hz, 1H), 3.78 (dd, J = ten.4, 5.9 Hz, 1H), three.72 (dd, J = ten.4, four.three Hz, 1H), 2.54 (br, 1H), 2.27 two.16 (m, 1H), 1.ten (s, 2H), 1.06 (d, J = 7.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) 135.6, 133.1, 129.eight, 127.8, 67.4, 65.five, 65.1, 39.4, 26.9, 19.two, 14.6. IR (CH2Cl2) n (cm-1) 3383, 3071, 2932, 2859, 2361, 1470, 1427, 1389, 1111. HRMS (ESI, TOF): m/z = 377.1710, calcd For C21H30ClO2Si [M+H]+ 377.1704. The diastereoselectivity was 1.0:ten determined by 1H NMR and confirmed by Chiral HPLC (Chiralcel OD, Hex/iPrOH 99:1, 1 mL/min, 25 ), tr 11.8 min (minor diastereomer), tr 12.
