Wolff Rearrangement of Oxidatively Generated α-Oxo Gold Carbenes: An Effective Approach to Silylketenes

Angewandte Chemie
Yang ZhengLiming Zhang

Abstract

Gold-catalyzed oxidations of alkynes by N-oxides offer direct access to reactive α-oxo gold carbene intermediates from benign and readily available alkynes instead of hazardous diazo carbonyl compounds. Despite various versatile synthetic methods developed based on this strategy, one of the hallmarks of α-oxo carbene/carbenoid chemistry, that is, the Wolff rearrangement, has not been realized in this context. This study discloses the first examples that show the Wolff rearrangement can be readily realized by α-oxo gold carbenes oxidatively generated from TBS-terminated alkynes (TBS=tert-butyldimethylsilyl). The thus-generated silylketenes can be either isolated pure or subsequently trapped by various internal or external nucleophiles in one pot to afford α-silylated carboxylic acids, their derivatives, or TBS-substituted allenes.

References

Mar 18, 2006·Beilstein Journal of Organic Chemistry·Stephen P Marsden, Pascal C Ducept
Jun 5, 2010·Journal of the American Chemical Society·Longwu YeLiming Zhang
Jun 8, 2011·Angewandte Chemie·Dhananjayan VasuRai-Shung Liu
Jul 5, 2011·Angewandte Chemie·Jian Xiao, Xingwei Li
Feb 3, 2012·Angewandte Chemie·Sabyasachi BhuniaRai-Shung Liu
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Jan 17, 2014·Accounts of Chemical Research·Liming Zhang
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Jan 20, 2016·Chemical Society Reviews·Zhitong ZhengLiming Zhang

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Citations

Jun 26, 2020·Angewandte Chemie·Zhitong ZhengLiming Zhang
Jan 22, 2021·Organic & Biomolecular Chemistry·Masato TsudaHiroyuki Nakamura
Feb 17, 2021·Chemical Reviews·Zhitong ZhengLiming Zhang
Jun 2, 2021·Organic & Biomolecular Chemistry·Guang-Xin RuGuang-Qin Gao
Jun 4, 2021·Organic Letters·Zixuan TongEdward A Anderson
Aug 14, 2020·Chemical Reviews·Long-Wu YeRai-Shung Liu

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