Photochemical Strain-Release Driven Cyclobutylation of C(sp3)-centered Radicals.
Photochemical Strain-Release Driven Cyclobutylation of C(sp3)-centered Radicals.
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DOI：
10.26434/chemrxiv.8323406.v1
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发表时间：
2019-06
影响因子：
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通讯作者：
G. Ernouf;E. Chirkin;L. Rhyman;P. Ramasami;J. Cintrat
中科院分区：
文献类型：
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作者：
G. Ernouf;E. Chirkin;L. Rhyman;P. Ramasami;J. Cintrat
描述了一种新的光氧化还原催化的官能化环丁烷脱羧自由基加成方法。该反应涉及以 C(sp3) 为中心的自由基与高度紧张的双环[1.1.0]丁烷的前所未有的正式 Giese 型加成反应。温和的光氧化还原条件利用了现成且稳定的苯磺酰基双环[1.1.0]丁烷，被证明适用于各种α-氨基和α-氧基羧酸，为1,3-二取代环丁烷提供了一条简洁的路线。此外，动力学研究和 DFT 计算揭示了双环[1.1.0]丁烷相对于相应烯烃体系反应性的机制细节。
A new photoredox-catalyzed decarboxylative radical addition approach to functionalized cyclobutanes is described. The reaction involves an unprecedented formal Giese-type addition of C(sp3)-centered radicals to highly strained bicyclo[1.1.0]butanes. The mild photoredox conditions, which make use of a readily available and bench stable phenyl sulfonyl bicyclo[1.1.0]butane, proved to be amenable to a diverse range of α-amino and α-oxy carboxylic acids, providing a concise route to 1,3-disubstituted cyclobutanes. Furthermore, kinetic studies and DFT calculations unveiled mechanistic details on bicyclo[1.1.0]butane reactivity relative to the corresponding olefin system.