Iron-Catalyzed Stereoconvergent Tertiary Alkylation of (E)- and (Z)-Mixed Internal Olefins with Functionalized Tertiary Alkyl Halides,ACS Catalysis

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Iron-Catalyzed Stereoconvergent Tertiary Alkylation of (E)- and (Z)-Mixed Internal Olefins with Functionalized Tertiary Alkyl Halides
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-09-01 , DOI: 10.1021/acscatal.1c03009
Yusei Nakashima ₁ , Junki Matsumoto ₁ , Takashi Nishikata ₁

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Herein, we report an efficient method for the stereoconvergent tertiary alkylations of (E)- and (Z)-mixed internal olefins (styrenes, enamides, and vinylic ethers) to produce trisubstituted olefins bearing a quaternary carbon center via an addition/elimination reaction in the presence of an iron catalyst. (E)- and (Z)-mixed internal olefins with various E/Z ratios reacted smoothly with α-bromocarbonyls as a tertiary alkyl source to exclusively produce (E)-trisubstituted olefins. Mechanistic studies revealed that each of the (E)- and (Z)-internal olefins exhibited the same reactivity, and the exclusive generation of (E)-trisubstituted olefin products could be attributed to the β-hydrogen elimination of an alkyl iron species. The developed method can be used to synthesize highly congested trisubstituted olefins containing a quaternary carbon atom that bears various alkyl chains.

中文翻译：

(E)-和(Z)-混合内烯烃与官能化叔烷基卤化物的铁催化立体会聚叔烷基化

在这里，我们报告了一种有效的方法，用于 ( E )- 和 ( Z )-混合内烯烃（苯乙烯、烯酰胺和乙烯基醚）的立体会聚叔烷基化，通过加成/消除反应生产带有季碳中心的三取代烯烃。铁催化剂的存在。( E )- 和 ( Z )-混合的内烯烃具有各种E / Z比，与作为叔烷基源的 α-溴羰基反应顺利，专门生产 ( E )-三取代烯烃。机理研究表明，( E )- 和 ( Z)-内烯烃表现出相同的反应性，并且 ( E )-三取代烯烃产物的唯一生成可归因于烷基铁物质的β-氢消除。所开发的方法可用于合成高度拥挤的三取代烯烃，其中含有带有各种烷基链的季碳原子。

更新日期：2021-09-17

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