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Synfacts 2006(6): 0577-0577  
DOI: 10.1055/s-2006-934471
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Nucleophilic Monofluoromethylation of Sulfinylimines

Contributor(s): Mark Lautens, Frédéric Ménard
Y. Li, C. Ni, J. Liu, L. Zhang, J. Zheng, L. Zhu, J. Hu*
Shanghai Institute of Organic Chemistry, P. R. of China
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Publication History

Publication Date:
19 May 2006 (online)

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Significance

The described method allows for the preparation of enantiomerically pure α-mono­fluoromethylamines by nucleophilic fluoromethylation of Ellman’s N-(tert-butanesulfinyl)imines (J. A. Ellman, T. D. Owens, T. P. Tang Acc. Chem. Res. 2002, 35, 984-995). Structurally diverse (R)-(tert-butanesulfinyl)imines 1 reacted with the (phenylsulfonyl)fluoromethyl anion to give the corresponding (phenylsulfonyl)fluoromethylated sulfinamides 2 in excellent chemical yields (for the first step) and high stereoselectivity (facial selectivity >98:2). Sulfinamides 2 were readily converted without purification into α-monofluoromethyl­amine salts 3 in good overall yields via reductive desulfonylation and removal of the tert-butanesulfinyl group. The same methodology was used to synthesize α-monofluoromethylated cyclic secondary amines by using tosylate-bearing (R)-(tert-butanesulfinyl)imines 4. The nitrogen-anion species of 4 generated from the first nucleophilic addition step was trapped intramolecularly in a nucleophilic addition-substitution tandem reaction.