通过立体选择性催化交叉复分解反应合成 Z-（频哪醇酯）烯丙基硼和 Z-（频哪醇酯）烯基硼化合物。
Synthesis of Z-(pinacolato)allylboron and Z-(pinacolato)alkenylboron compounds through stereoselective catalytic cross-metathesis.
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
出版信息
J Am Chem Soc. 2013 Apr 24;135(16):6026-9. doi: 10.1021/ja403188t. Epub 2013 Apr 15.
Abstract
The first examples of catalytic cross-metathesis (CM) reactions that furnish Z-(pinacolato)allylboron and Z-(pinacolato)alkenylboron compounds are disclosed. Products are generated with high Z selectivity by the use of a W-based monoaryloxide pyrrolide (MAP) complex (up to 91% yield and >98:2 Z:E). The more sterically demanding Z-alkenylboron species are obtained in the presence of Mo-based MAP complexes in up to 93% yield and 97% Z selectivity. Z-selective CM with 1,3-dienes and aryl olefins are reported for the first time. The utility of the approach, in combination with catalytic cross coupling, is demonstrated by a concise and stereoselective synthesis of anticancer agent combretastatin A-4.
摘要
首次披露了催化交叉复分解（CM）反应的实例，这些反应提供了 Z-（频哪醇）烯丙基硼和 Z-（频哪醇）烯基硼化合物。通过使用基于 W 的单芳氧基吡咯烷（MAP）配合物（高达 91%的产率和> 98:2 Z:E），可以高 Z 选择性地生成产物。在存在基于 Mo 的 MAP 配合物的情况下，更具空间位阻的 Z-烯基硼物种以高达 93%的产率和 97%的 Z 选择性获得。首次报道了 Z-选择性的 CM 与 1,3-二烯和芳基烯烃的反应。该方法与催化交叉偶联的结合，通过抗癌剂 combretastatin A-4 的简洁和立体选择性合成得到了证明。
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