Department of Chemistry, KAIST, 373-1 Gusung Dong, Yuseong, Daejeon, 305-701, Korea.
Chem Asian J. 2011 Feb 1;6(2):646-51. doi: 10.1002/asia.201000672. Epub 2010 Nov 12.
A thorough study on the diastereoselectivity in the TMM diyl mediated [2+3] cycloaddition reaction of monosubstituted linear substrates to form angularly fused triquinanes was carried out. Substitution at position 3 provided complete diastereoselectivity, while positions 1 and 4 induced marginal stereoselectivity. Position 2 did not show any influence on the diastereoselectivity. Position 4 turned out to be incompatible with the cycloaddition reaction as the carbene intermediate underwent O-Si bond insertion to form a dihydrofuran ring.
对 TMM 二基介导的单取代线性底物[2+3]环加成反应形成角并合的三奎烷的非对映选择性进行了深入研究。在 3 位取代可提供完全的非对映选择性，而 1 位和 4 位取代则诱导出一定的立体选择性。2 位取代对非对映选择性没有影响。4 位取代与环加成反应不兼容，因为卡宾中间体发生 O-Si 键插入形成二氢呋喃环。
