Rhodium(I)-Catalyzed Highly Enantioselective Insertion of Carbenoid into Si-H: Efficient Access to Functional Chiral Silanes

Journal of the American Chemical Society
Diao ChenDong-Xing Zhu

Abstract

The first rhodium(I)-catalyzed enantioselective Si-H insertion reaction of α-diazoesters and α-diazophosphonates has been developed. The use of a C1-symmetric chiral diene ligand enabled the asymmetric reaction to proceed under exceptionally mild conditions and give versatile chiral α-silyl esters and phosphonates with excellent enantioselectivities (up to 99% ee). The mechanism and stereochemical pathway of this novel Rh(I)-carbene-directed Si-H insertion was investigated by deuterium kinetic isotope effect experiments and DFT calculations.

References

Oct 27, 1995·Journal of Medicinal Chemistry·D V PatelE W Petrillo
Feb 19, 2002·Chemical Reviews·Ian FlemingDavid Walter
Jun 25, 2003·Drug Discovery Today·Graham A Showell, John S Mills
Apr 6, 2007·Organic Letters·Freeman M WongWeiming Wu
May 7, 2008·Angewandte Chemie·Christian DefieberErick M Carreira
Oct 1, 2008·Angewandte Chemie·Yong-Zhen ZhangQi-Lin Zhou
Mar 18, 2010·Journal of the American Chemical Society·Yoichi YasutomiTsutomu Katsuki
Jun 4, 2010·Journal of the American Chemical Society·Ramya Sambasivan, Zachary T Ball
May 4, 2012·The Journal of Organic Chemistry·Stefan AbeleChristian Moessner
Oct 16, 2012·Journal of Medicinal Chemistry·Annaliese K Franz, Sean O Wilson
Jan 5, 2013·Angewandte Chemie·Virginie CirriezOlivier Riant
Feb 20, 2014·Chemical Communications : Chem Comm·Yi Li, Ming-Hua Xu
Apr 29, 2014·Journal of the American Chemical Society·Akira YadaMasahiro Murakami

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Citations

Feb 26, 2016·Journal of the American Chemical Society·Christophe WerléAlois Fürstner
Jan 31, 2017·The Journal of Organic Chemistry·Hoda KeipourThierry Ollevier
May 13, 2017·The Journal of Organic Chemistry·Shinya KogaHiroshi Nishihara
Feb 12, 2017·Chemical Communications : Chem Comm·Zhaohong LiuXihe Bi
Mar 18, 2017·Chemical Communications : Chem Comm·Yoko NakagawaSeiji Iwasa
Mar 2, 2017·Organic & Biomolecular Chemistry·Kankanala Ramakrishna, Chinnappan Sivasankar
Feb 16, 2017·Angewandte Chemie·Stephan Lütz
Jun 24, 2017·Organic & Biomolecular Chemistry·Hoda KeipourThierry Ollevier
Jun 28, 2017·Journal of the American Chemical Society·Biao ChengZhan Lu
Sep 25, 2018·Chemical Communications : Chem Comm·Zhenxing LiuJianbo Wang
Dec 19, 2018·Angewandte Chemie·Mauro Mato, Antonio M Echavarren
Aug 21, 2019·ChemCatChem·Rahul L KhadeYong Zhang
Jul 16, 2019·Chemistry : a European Journal·Yong Zhang
Nov 26, 2016·Science·Hendrik F T Klare, Martin Oestreich
Apr 9, 2021·Journal of the American Chemical Society·Santanu SinghaAlois Fürstner
Apr 29, 2021·Journal of the American Chemical Society·Marc Garcia-BorràsK N Houk
Jun 30, 2021·The Journal of Organic Chemistry·Liang-Liang YangQi-Lin Zhou
Jul 9, 2021·Journal of the American Chemical Society·Mauro MatoAntonio M Echavarren
Aug 13, 2021·Journal of the American Chemical Society·Jingfeng HuoJianbo Wang
Oct 14, 2017·Organic Letters·Hoda Keipour, Thierry Ollevier
Mar 29, 2018·Journal of the American Chemical Society·Biao ChengZhan Lu
Oct 9, 2018·Organic Letters·Haorui GuXufeng Lin
Jun 28, 2018·Organic Letters·Marios Kidonakis, Manolis Stratakis
Dec 5, 2017·Journal of the American Chemical Society·Julie L HofstraSarah E Reisman

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