State key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , 555 Zuchongzhi Road, Shanghai 201203, China.
Org Lett. 2014 May 16;16(10):2712-5. doi: 10.1021/ol500993h. Epub 2014 Apr 28.
The first Rh-catalyzed asymmetric tandem cyclization of nitrogen- or oxygen-bridged 5-alkynones with arylboronic acids was achieved. The simple catalytic system involving a rhodium(I) complex with readily available chiral BINAP ligand promotes the reaction to proceed in a highly stereocontrolled manner. This protocol provides a very reliable and practical access to a variety of chiral heterocyclic tertiary allylic alcohols possessing a tetrasubstituted carbon stereocenter and an all-carbon tetrasubstituted olefin functionality in good yields with great enantioselectivities up to 99% ee.
首次实现了氮桥或氧桥 5-炔酮与芳基硼酸的 Rh 催化不对称串联环化反应。该反应涉及一种简单的催化体系，其中含有易得的手性 BINAP 配体的铑（I）配合物，可促进反应以高度立体控制的方式进行。该方案为各种手性杂环叔烯丙基醇提供了一种非常可靠和实用的合成途径，这些醇具有四取代碳立体中心和全碳四取代烯烃官能团，产率高，对映选择性高达 99%ee。
