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. 2012 Apr 16;51(16):3923-7.
doi: 10.1002/anie.201109044. Epub 2012 Mar 5.

Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer

Michael T Bovino  1 , Sherry R Chemler
Affiliations

Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer

Michael T Bovino et al. Angew Chem Int Ed Engl. .

Abstract

Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence.

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Figures

Scheme 1
Scheme 1
Aminohalogenation by atom transfer. Tf = trifluoromethyl-sulfonyl.
Scheme 2
Scheme 2
Substitution reactions of the chiral alkyliodide. acac = acetoacetonate, DMF = N,N′-dimethylformamide, HMTA = hexamethylene-tetramine, TMEDA= N,N,N′,N′-tetramethylethylenediamine.
Scheme 3
Scheme 3
Enantioselective aminochlorination and aminobromination.
See this image and copyright information in PMC

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