The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Org Biomol Chem. 2012 Aug 14;10(30):5803-6. doi: 10.1039/c2ob25121c. Epub 2012 Mar 8.
The combined carbometalation-zinc homologation-allylation reaction of the resulting stereodefined 3,3-disubstituted allylmetal species with ketones allow the preparation of allylic vicinal diol derivatives in good yields with excellent diastereomeric ratios from commercially available alkynes. Two adjacent quaternary centers are formed with the concomitant formation of three new carbon-carbon bonds in a single-pot operation in an acyclic system. The bulky substituent of the ketone occupies a pseudo-axial position in the Zimmerman-Traxler transition state.
生成的立体定义的 3,3-二取代烯丙基金属物种与酮的羰基-金属化-锌同系化反应允许通过商业可得的炔烃以良好的收率和优异的非对映选择性制备烯丙基顺式二醇衍生物。在非环体系中单步操作中形成两个相邻的季碳原子，同时形成三个新的碳-碳键。酮的大取代基在齐默曼-特拉克斯勒过渡态中占据拟轴向位置。
