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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Typical procedure for the preparation
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[²]
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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
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