Scope and mechanistic insight into the chemistry of cyanocarbenes derived from alkynyl triazenes by UV irradiation†

Melina Maag , Linus Bjarne Dittmer , Elena Michel , Alexandra V. Mackenroth , Martin C. Dietl , Frank Rominger , Matthias Rudolph , Andreas Dreuw , A. Stephen K. Hashmi
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Abstract

Herein we disclose a systematic evaluation of the scope and limitations for the use of alkynyl triazenes for the synthesis of cyano-substituted cyclopropanes and cyclopropenes. The method is based on the formation of a cyanocarbene by cleavage of the N1–N2 bond of the alkynyl triazene precursor under UV light, which then reacts with a styrene or alkyne to form the respective products, making this a simple approach avoiding metals typically used in related reactions of organic azides. Different substituents on the triazene moiety, N-terminus and styrene/alkyne were investigated concerning their influence on the yield and diastereoselectivity with respect to the resulting cyclopropanes. The study showed that electron-rich aryl substituents at the alkynyl triazenes enable a good diastereomeric excess favouring the anti-diastereomer. Accompanying computational studies revealed that this diastereomeric preference can be qualitatively predicted from the relative stability of the singlet and triplet states of the cyanocarbene, as well as the dispersive attraction between the carbene and the olefin.

Abstract Image

紫外光照射从炔基三氮杂烯衍生的氰碳烯的范围和机理研究
在此,我们公开了对炔基三氮杂烯用于合成氰基取代环丙烷和环丙烯的范围和限制的系统评价。该方法是基于在紫外光下通过切割炔基三氮烯前驱体的N1-N2键来形成氰碳烯,然后与苯乙烯或炔反应生成相应的产物,这使得该方法简单,避免了在有机叠氮化物的相关反应中通常使用的金属。考察了三氮端、n端和苯乙烯/炔上不同取代基对生成的环丙烷的产率和非对映选择性的影响。研究表明,富电子的芳基取代基在炔基三氮杂烯上形成了良好的非对映体过剩,有利于抗非对映体。伴随的计算研究表明,这种非对映体的偏好可以定性地从单线态和三重态的相对稳定性,以及碳烯和烯烃之间的分散吸引力预测。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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CiteScore
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