PMID: 11312937Apr 21, 2001Paper

Beta-trimethylsilyl cyclopropylcarbenes

The Journal of Organic Chemistry
Xavier Creary, M A Butchko

Abstract

Thermal decomposition of the in situ generated lithium salt of the tosylhydrazone derivative of cyclopropyl trimethylsilylmethyl ketone gave 1-cyclopropyl-1-trimethylsilylethylene, a product of exclusive silyl migration. Thermal decomposition of the sodium salts of tosylhydrazone derivatives of 1-trimethylsilylcyclopropyl alkyl ketones also gave methylenecyclopropane products derived from trimethylsilyl migration. These reactions were interpreted in terms of rapid trimethylsilyl migration to carbene-like centers that compete effectively with ring expansion processes of cyclopropylcarbenes. Computational studies (B3LYP/6-31G) suggest that cyclopropyl stabilization of carbenes is more effective than beta-trimethylsilyl stabilization. However, beta-trimethylsilyl stabilized conformations are easily attained, and these conformations can lead to silyl migrations. There are two minimum energy conformations of methyl-1-trimethylsilylcyclopropylcarbene, 27, and the rotational barrier to interconversion of these conformations (5.4 kcal/mol) is substantially lower than in the parent cyclopropylcarbene (15 kcal/mol). The onset of a stabilizing interaction in the transition state between the carbene vacant orbital with the adjacent Si-C si...Continue Reading

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Citations

Oct 27, 2015·The Journal of Organic Chemistry·Xavier Creary
May 12, 2006·Organic & Biomolecular Chemistry·Sambasivarao KothaRaghavan B Sunoj
Aug 23, 2019·Beilstein Journal of Organic Chemistry·Xavier Creary
Dec 3, 2009·The Journal of Organic Chemistry·Xavier Creary, Elizabeth D Kochly
Feb 11, 2009·The Journal of Organic Chemistry·Xavier Creary, Elizabeth D Kochly
Jul 28, 2018·Journal of the American Chemical Society·Brandon E HainesDjamaladdin G Musaev
Mar 27, 2013·Journal of the American Chemical Society·Xavier Creary
Feb 20, 2014·The Journal of Organic Chemistry·Xavier Creary, Anna Heffron
Jan 7, 2015·The Journal of Organic Chemistry·Xavier CrearyMariana Prado
Jan 5, 2002·The Journal of Organic Chemistry·Xavier Creary, Mark A Butchko
May 11, 2002·The Journal of Organic Chemistry·Robin A FarlowChristopher M Hadad
Apr 5, 2007·The Journal of Organic Chemistry·Xavier CrearyMarie Vervaeke

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