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Synlett 2011(18): 2681-2684  
DOI: 10.1055/s-0031-1289531
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Diastereoselective Synthesis of Enantiopure Homopropargylic N-tert-Butylsulfinylamines

Mathieu Cyklinsky, Candice Botuha, Fabrice Chemla*, Franck Ferreira, Alejandro Pérez-Luna
UPMC-Univ Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), Institut de Chimie Moléculaire (FR 2769), case 183, 4 place Jussieu, 75005 Paris Cedex 05, France
Fax: +33(1)44277567; e-Mail: fabrice.chemla@upmc.fr;
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Publication History

Received 21 June 2011
Publication Date:
19 October 2011 (online)

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Abstract

The diastereoselective synthesis of enantiopure homopropargylic amines by propargylation of various N-tert-butylsulfinylimines (tBS-imines) with 1-trimethylsilyl allenylzinc bromide is presented.

Key words

amines - asymmetric synthesis - chiral auxiliaries - im­ines - zinc

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12

Typical procedure for the preparation of 3a-h (Table  [²] ): To a solution of 1-trimethylsilylpropyne (296 µL, 2.00 mmol) in THF (7 mL) was added s-BuLi (1.3 m in pentane, 1.54 mL, 2.00 mmol) at such a rate that the internal temperature did not exceed -45 ˚C. When the addition was complete, the reaction mixture was warmed to -20 ˚C over a period of 20 min. After 45 min of stirring at -20 ˚C, the reaction mixture turned bright yellow and was cooled to -35 ˚C prior to the addition of ZnBr2 (1 M in THF, 2.00 mL, 2.00 mmol) over a period of 5 min. After 30 min stirring at -35 ˚C, the resulting colorless mixture was cooled to -78 ˚C (for 2a) or warmed to 20 ˚C (for 2b-h). Sulfinylimine 2a-h (1.00 mmol) in THF (1 mL) was then added dropwise. The reaction mixture was stirred at r.t. until the reaction was complete (reaction monitored by TLC; ˜30 min) then quenched by addition of NH4Cl/NH3 (2:1), extracted with Et2O, dried (MgSO4), and concentrated to give 3a-h, which were purified by flash chromatography over silica gel