反应详情

A solution of p-toluenesulfonyl chloride (252 mg, 1.32 mmol) in pyridine (7.0 mL), alcohol (17) (290 mg, 1.10 mmol) was stirred at 24° C. for 2 days then diluted with water (15 mL). The product was extracted into tert-butyl methyl ether (3×20 mL) then dried (MgSO4), filtered and reduced in vacuo. Flash chromatography over silica, eluting with ethyl acetate:heptane mixtures 7:93 to 20:80 gave tosylate (32) (282 mg, 61%) as a colourless oil. TLC (Rf=0.35, EtOAc:heptane 1:1), analytical HPLC single main peak, Rt=19.02 min., HPLC-MS 418.2 [M+H]+, 857.3 [2M+Na]+; [α]D11 −86.1° (c=1.103, CHCl3; δH (500 MHz, CDCl3) 2.37 (3H, s, aryl-CH3), 3.29-3.37 and 3.50-3.56 (2H total, m, CH2NH), 4.53-4.56 (2H total, m, OCH2CH═CH), 4.62-4.66 m, OCHCH═CH), 4.85-4.90 (1H, m, CHOTs), 5.02-5.08 (2H, m, OCH2Ph), 5.02 (1H, brs, NH), 5.65-5.70 and 5.94-5.98 (2H total, m, CH2CH═CH), 7.27 (2H, d, J=8.12 Hz, aromatic CH3CCH), 7.29-7.37 (5H, m, phenyl CH), 7.76 (2H, d, J=8.23 Hz, aromatic OSO2CCH); δC (125 MHz, CDCl3) 21.609 (aryl-CH3), 41.749 (CH2NHCbz), 66.833 (CH2Ph), 75.939 (OCH2CH═CH), 81.235 (CHOTs), 85.203 (OCHCH═CH), 124.702, 127.887, 128.026, 128.128, 128.504, 129.687 and 129.757 (OCH2CH═CH and aromatic CH), 133.591 (CHOSO2C quaternary), 136.368 (Cbz quaternary), 144.906 (CH3C quaternary), 156.271 (Cbz C═O).

1. extractionThe product was extracted into tert-butyl methyl ether (3×20 mL)
2. dry with materialthen dried (MgSO4)
3. filtrationfiltered
4. washFlash chromatography over silica, eluting with ethyl acetate