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铜催化的γ选择性烯丙基-烷基偶联反应:烯丙基磷酸酯与烷基硼烷之间的反应。

Copper-catalyzed gamma-selective allyl-alkyl coupling between allylic phosphates and alkylboranes.

机构信息

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.

出版信息

J Am Chem Soc. 2010 Mar 10;132(9):2895-7. doi: 10.1021/ja9109105.

Abstract

Copper-catalyzed allyl-alkyl coupling between allylic phosphates and alkylboranes, prepared by hydroboration of alkenes with 9-BBN-H, takes place with complete gamma- and E-selectivities and with preferential 1,3-anti stereochemistry. The reaction tolerates various functional groups in both the allylic phosphate and alkylborane. Catalytic mechanisms involving transmetalation between a trialkyl(alkoxo)borate and a copper(I) complex to form an alkylcopper(I) species are proposed.

摘要

铜催化的烯丙基膦盐与烷基硼烷的烯丙基-烷基偶联反应,通过烯烃与 9-BBN-H 的硼氢化反应制备,具有完全的γ和 E 选择性,并具有优先的 1,3-反立体化学选择性。该反应在烯丙基膦盐和烷基硼烷中均能耐受各种官能团。提出了涉及三烷基(烷氧基)硼酸酯与铜(I)配合物之间的转金属化反应,以形成烷基铜(I)物种的催化机制。

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