用TiCl4-路易斯碱配合物脱除叔丁基二甲基硅基醚的高效方法：在1β-甲基碳青霉烯合成中的应用

Efficient method for the deprotection of tert-butyldimethylsilyl ethers with TiCl4-Lewis base complexes: application to the synthesis of 1beta-methylcarbapenems.

作者信息

Iida Akira, Okazaki Hiroki, Misaki Tomonori, Sunagawa Makoto, Sasaki Akira, Tanabe Yoo

机构信息

Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.

出版信息

J Org Chem. 2006 Jul 7;71(14):5380-3. doi: 10.1021/jo0604484.

DOI:10.1021/jo0604484

PMID:16808532

Abstract

TiCl4-Lewis base (AcOEt, CH3NO2) complexes smoothly deprotected tert-butyldimethylsilyl (TBDMS) ethers. The reaction velocity with these complexes, which seemed less reactive due to the influence of Lewis bases, was considerably greater than that with TiCl4 alone. Selective desilylations between aliphatic and aromatic TBDMS ethers (1 and 5), between 1 and benzyl, allyl, tosyl, methoxyphenyl, and chloroacetyl ethers (13, 14, 15, 16, and 17), and between TBDMS and TBDPS ethers (18 and 19) were successfully performed. Desilylation of TBDMS-aldol, acyloin, and beta-lactam analogues 9-12 proceeded smoothly due to anchimeric assistance by the neighboring carbonyl groups. The present method was successfully applied to the practical synthesis of 1beta-methylcarbapenems 20a'-f'.

摘要

四氯化钛-路易斯碱（乙酸乙酯、硝基甲烷）配合物能顺利地脱除叔丁基二甲基硅基（TBDMS）醚。这些配合物的反应速度，因路易斯碱的影响看似活性较低，却比单独使用四氯化钛时快得多。脂肪族和芳香族TBDMS醚（1和5）之间、1与苄基、烯丙基、甲苯磺酰基、甲氧基苯基及氯乙酰基醚（13、14、15、16和17）之间，以及TBDMS与TBDPS醚（18和19）之间的选择性脱硅反应均成功实现。由于相邻羰基的邻基协助作用，TBDMS-羟醛、偶姻及β-内酰胺类似物9 - 12的脱硅反应顺利进行。本方法成功应用于1β-甲基碳青霉烯20a'-f'的实际合成。