A smooth rearrangement of N-p-toluenesulfonyl 2-tert-butyldiphenylsilylmethyl-substituted azetidines into N-p-toluenesulfonyl 3-tert-butyldiphenylsilyl-substituted pyrrolidines

Organic & Biomolecular Chemistry
Bharat D NarheVeejendra K Yadav

Abstract

The rearrangement of N-p-toluenesulfonyl 2-tert-butyldiphenylsilylmethyl-substituted azetidines into 3-tert-butyldiphenylsilyl-substituted pyrrolidines under Lewis acid conditions in dichloromethane involves 1,2-migration of silicon through a siliranium ion. The formation of siliranium ion was discovered not to be in concert with σ(C-N) cleavage from stereochemical analysis of the pyrrolidine products formed from 3- and 4-substituted-2-tert-butyldiphenylsilylmethyl azetidines and also from the optical rotation data and chiral HPLC analysis of the pyrrolidine product formed from N-p-toluenesulfonyl 2(R)-tert-butyldiphenylsilylmethyl azetidine. The formation of sterically less hindered siliranium ion is followed by its S(N)2 opening by the internal nitrogen nucleophile. Oxidative cleavage of σ(C-Si) bond leads to the formation of 3-hydroxypyrrolidines.

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Citations

Jul 23, 2016·The Journal of Organic Chemistry·Alpa K PancholiMichael Shipman
Jul 30, 2015·Organic & Biomolecular Chemistry·Manas K GhoraiAmit Kumar

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