The alpha-effect in gas-phase SN2 reactions revisited.

Org Lett

College of Chemistry, Sichuan University, Chengdu, PR China.

Published: January 2006

This paper re-examines gas-phase S(N)2 reactions at saturated carbon for model reactions Nu(-) + CH(3)Cl --> CH(3)Nu + Cl(-) (Nu(-) = HO(-), MeO(-), NH(2)(-), HS(-), Cl(-), Br(-), I(-), HOO(-), MeOO(-), HSS(-), and NH(2)NH(-)) using the G2(+) theory. The calculated results show that the alpha-effect does exist in the gas-phase S(N)2 reaction at the sp(3) carbon, contrary to the currently accepted notion of the absence of the alpha-effect in the gas phase.

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http://dx.doi.org/10.1021/ol0526930DOI Listing

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