Racemization of optically active dichloromethyl p-tolyl sulfoxide took place at −78 • C in the presence of potassium bis(trimethylsilyl)amide (KHMDS), while the same racemization did not occur under reflux in toluene in the absence of KHMDS. Density functional theory calculations suggested that the pyramidal inversion at the sulfur center was unlikely to be involved in the racemization mechanism. An anionic species of the sulfoxide was found to be gradually converted into chlorobis(p-tolylsulfinyl)methane and dichlorocarbene. We propose a racemization mechanism mediated by achiral potassium p-toluenesulfenate and chloro(p-tolylsulfinyl)methylene. C 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:131-137, 2013; View this article online at wileyonlinelibrary.com.
Synthesis of 3-Azabicyclo[3.1.0]hexanes by Insertion of Cyclopropylmagnesium Carbenoids into an Intramolecular C-H Bond Adjacent to a Nitrogen Atom. -Starting from 1-chlorocyclopropyl para-tolylsulfoxides bearing an N,N-disubstituted aminomethyl group the title reaction is performed with high yield. The site-selectivity in the transformation of substrates with an unsymmetrically N,N'-disubstituted aminomethyl group is examined. The reaction is not applicable to N,N-disubstituted aminoethyl group-containing substrates. Enantioenriched substrates are shown to deliver the corresponding products with high enantiomeric excess. -(KIMURA*, T.; WADA, N.; TSURU, T.; SAMPEI, T.; SATOH, T.; Tetrahedron 71 (2015) 35, 5952-5958, http://dx.
On treatment with iPr—MgCl, a variety of 1‐chlorocyclopropyl p‐tolyl sulfoxides bearing an ether functional group at the 2‐ or 4‐position of the alkyl side chain gives the bicyclic title compounds.
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