The combined C-H functionalization/Cope rearrangement: discovery and applications in organic synthesis.

Accounts of Chemical Research
Huw M L Davies, Yajing Lian

Abstract

The development of methods for the stereoselective functionalization of sp(3) C-H bonds is a challenging undertaking. This Account describes the scope of the combined C-H functionalization/Cope rearrangement (CHCR), a reaction that occurs between rhodium-stabilized vinylcarbenoids and substrates containing allylic C-H bonds. Computational studies have shown that the CHCR reaction is initiated by a hydride transfer to the carbenoid from an allyl site on the substrate, which is then rapidly followed by C-C bond formation between the developing rhodium-bound allyl anion and the allyl cation. In principle, the reaction can proceed through four distinct orientations of the vinylcarbenoid and the approaching substrate. The early examples of the CHCR reaction were all highly diastereoselective, consistent with a reaction proceeding via a chair transition state with the vinylcarbenoid adopting an s-cis conformation. Recent computational studies have revealed that other transition state orientations are energetically accessible, and these results have guided the development of highly stereoselective CHCR reactions that proceed through a boat transition state with the vinylcarbenoid in an s-cis configuration. The CHCR reaction has broad...Continue Reading

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Citations

Sep 24, 2013·Chemical Reviews·Illan J Kramer, Edward H Sargent
Oct 27, 2012·Journal of the American Chemical Society·Austin G Smith, Huw M L Davies
Aug 7, 2013·Journal of the American Chemical Society·Joshua S AlfordHuw M L Davies
Sep 13, 2013·Journal of the American Chemical Society·Changming Qin, Huw M L Davies
Feb 26, 2016·Journal of the American Chemical Society·Christophe WerléAlois Fürstner
Apr 7, 2016·Accounts of Chemical Research·Dean J Tantillo
Jul 8, 2015·Journal of the American Chemical Society·Xin HongMatthias Brewer
Apr 12, 2016·Journal of the American Chemical Society·Liangbing FuHuw M L Davies
Oct 25, 2016·Ultrasonics Sonochemistry·Bubun Banerjee
Apr 11, 2017·Chemical Communications : Chem Comm·RahulKumar Rajmani Singh, Rai-Shung Liu
Aug 17, 2016·Chemistry : a European Journal·Celia A Incerti-PradillosAndrei V Malkov
Jul 6, 2014·Chemical Communications : Chem Comm·Wanxing ShaJiang Cheng
Jan 18, 2017·Chemistry : a European Journal·Liangbing FuHuw M L Davies
Dec 15, 2015·Chemical Society Reviews·Lu Liu, Junliang Zhang
Aug 16, 2016·Organic & Biomolecular Chemistry·Chuo Chen
Oct 28, 2017·Chemical Communications : Chem Comm·Kiran ChinthapallyIndrajeet Sharma
Jun 9, 2015·Chemical Society Reviews·Andrew G Schafer, Simon B Blakey
Jan 13, 2015·Organic & Biomolecular Chemistry·Arvind K Yadav, Lal Dhar S Yadav
Aug 1, 2015·Chemistry : a European Journal·Chenghao ZhuJiangtao Sun

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