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立体选择性环丁烯醇合成:烯丙醇的非均相钯催化氧化环化-硼化反应。

Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols.

机构信息

Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.

Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.

出版信息

Chemistry. 2019 Jan 2;25(1):210-215. doi: 10.1002/chem.201805118. Epub 2018 Nov 5.

DOI:10.1002/chem.201805118
PMID:30307089
Abstract

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.

摘要

一种高效、高选择性的钯固载于氨基功能化硅介孔泡沫(Pd-AmP-MCF)催化的烯丙醇的氧化环化/硼化反应被开发用于非对映选择性环丁烯醇的合成。该多相钯催化剂可以回收并循环使用,没有观察到活性或选择性的损失。反应的高非对映选择性被认为源于烯丙醇羟基的导向效应。通过动力学拆分得到的手性烯丙醇,采用多相策略实现了光学纯环丁烯醇的合成。

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