Franzoni Ivan, Guénée Laure, Mazet Clément
University of Geneva, Department of Organic Chemistry, 30 quai Ernest Ansermet, 1211 Geneva-4, Switzerland.
Org Biomol Chem. 2015 Jun 14;13(22):6338-43. doi: 10.1039/c5ob00702j.
A palladium-catalyzed benzylation of α-branched aldehydes has been developed using benzyl methyl carbonates. The method gives access to congested quaternary centers in the vicinity of one of the most sensitive carbonyl functionalities and displays unprecedented generality with respect to both coupling partners. Evidence for the direct involvement of a Pd-η(3)-benzyl intermediate is provided. Extension of this strategy to the γ-benzylation of α,β-unsaturated aldehydes is further demonstrated.
已开发出一种使用碳酸苄基甲酯的钯催化α-支链醛的苄基化反应。该方法能够在最敏感的羰基官能团之一附近构建拥挤的季碳中心，并且对两种偶联伙伴均显示出前所未有的通用性。提供了Pd-η(3)-苄基中间体直接参与反应的证据。进一步证明了该策略扩展至α,β-不饱和醛的γ-苄基化反应。
