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Synthesis Of 2,4-, 3,4- And 2,3,4-substituted Pyrrolidines By Cyclization Of Neutral C-centered α-aminoalkyl Radicals

F. Bustos, José M. Gorgojo, Rubén Suero, J. Aurrecoechea
Published 2002 · Chemistry

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Abstract The effect of substitution at C-3 or C-4 of the 2-azahex-5-enyl chain has been studied in the SmI2-promoted cyclizations of neutral α-aminoalkyl radicals generated from N-(α-benzotriazolyl)alkenylamines. 2,4-, 3,4- and 2,3,4-substituted pyrrolidines are obtained in this manner in uniformly high yields but with stereoselectivities which depend markedly on the substitution pattern. Thus, a methyl substituent at C-4 (hex-5-enyl numbering) effectively controls the stereochemistry over three contiguous stereogenic centers whereas substituents at C-3 are found to exert a very poor control. Stereochemical results are rationalized according to the existing models for radical ring-closures.
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