Regioselective Simmons–Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis†,Chemical Science

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Regioselective Simmons–Smith-type cyclopropanations of polyalkenes enabled by transition metal catalysis†
Chemical Science ( IF 7.6 ) Pub Date : 2018-01-02 00:00:00 , DOI: 10.1039/c7sc04861k
Jacob Werth _{1,

2,

3,

4} , Christopher Uyeda _{1,

2,

3,

4}

Affiliation

A [^i−PrPDI]CoBr₂ complex (PDI = pyridine-diimine) catalyzes Simmons–Smith-type reductive cyclopropanation reactions using CH₂Br₂ in combination with Zn. In contrast to its non-catalytic variant, the cobalt-catalyzed cyclopropanation is capable of discriminating between alkenes of similar electronic properties based on their substitution patterns: monosubstituted > 1,1-disubstituted > (Z)-1,2-disubstituted > (E)-1,2-disubstituted > trisubstituted. This property enables synthetically useful yields to be achieved for the monocyclopropanation of polyalkene substrates, including terpene derivatives and conjugated 1,3-dienes. Mechanistic studies implicate a carbenoid species containing both Co and Zn as the catalytically relevant methylene transfer agent.

中文翻译：

过渡金属催化实现的区域选择性席梦斯-史密斯式聚烯烃环丙烷化†

A [^我-Pr PDI] COBR ₂络合物（PDI =吡啶二亚胺）催化使用CH西蒙斯-史密斯型还原环丙烷化反应₂溴₂在用Zn组合。与它的非催化变体相反，钴催化的环丙烷化能够基于其取代方式来区分具有类似电子性质的烯烃：单取代> 1,1-二取代>（Z）-1,2-二取代>（E）-1,2-二取代>三取代。该性质使得对于包括萜烯衍生物和共轭的1，3-二烯的聚烯烃底物的单环丙烷化，可以获得合成上有用的产率。机理研究表明，含有钴和锌作为催化相关的亚甲基转移剂的类胡萝卜素物质。

更新日期：2018-01-02

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