通过亚胺的不对称烯丙基硼化反应合成β-硅基化高炔丙基胺

Beta-silylated homopropargylic amines via the asymmetric allenylboration of aldimines.

作者信息

Gonzalez Ana Z, Soderquist John A

机构信息

Department of Chemistry, University of Puerto Rico, Rio Piedras, Puerto Rico 00931-3346, USA.

出版信息

Org Lett. 2007 Mar 15;9(6):1081-4. doi: 10.1021/ol070074g. Epub 2007 Feb 13.

DOI:10.1021/ol070074g

PMID:17295500

Abstract

The asymmetric synthesis of alpha-trimethylsilylpropargylic carbamines (7) through the addition of allenylboranes 4 to N-H aldimines is reported. The insertion of TMSCHN2 into enantiomerically pure B-alkynyl-10-TMS-9-borabicyclo[3.3.2]decanes 3 followed by a sterically driven 1,3-suprafacial borotropic shift proceeds with complete stereospecificity to produce 4 in diastereomerically and enantiomerically pure form. These reagents give 7 (51-85%, syn/anti >99%, 92-9% ee) permitting the recovery of 8 (53-63%). Allenylboranes 4 also provide a convenient route to optically pure allenylsilanes 13 (55-94%) through their protonolysis. [reaction: see text]

摘要

报道了通过将烯丙基硼烷4加成到N-H醛亚胺上不对称合成α-三甲基硅基炔丙基碳胺（7）的方法。将TMSCHN2插入对映体纯的B-炔基-10-TMS-9-硼双环[3.3.2]癸烷3中，随后通过空间驱动的1,3-超面硼迁移，以完全的立体专一性进行，生成非对映体纯和对映体纯形式的4。这些试剂得到7（51-85%，顺式/反式>99%，92-9% ee），并可回收8（53-63%）。烯丙基硼烷4还通过质子解反应为光学纯的烯丙基硅烷13（55-94%）提供了一条便捷的路线。[反应：见正文]