Diastereoselective Synthesis of trans-Ethynyl N-tert-Butanesulfinylaziridines [1]

Abstract

The condensation of allenylzinc (±)-1 onto N-tert-butanesulfinimines (±)-2 leads to the corresponding trans-ethynyl N-sulfinylaziridines with an excellent diastereoselection.

Key words

aziridines - asymmetric synthesis - carbenoid - chiral resolution - zinc

1

Propargylic Carbenoids, Part 3. For Part 2 see ref. 10a.

References

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1

Propargylic Carbenoids, Part 3. For Part 2 see ref. 10a.

13

Typical Procedure for the Synthesis of Ethynyl N -Sulfinylaziridines (±)-3: To a 0.1 M etheral solution of 3-chloro-1-trimethylsilylpropyne (1.0 equiv) under nitrogen atmosphere TMEDA (1.0 equiv) and n-BuLi (2.2 M in hexanes, 1.0 equiv) were successively added at -95 °C. The yellow solution was stirred 5 min at -95 °C and an 1.0 M etheral solution of ZnBr₂ (1.0 equiv) was added dropwise. The resulting white suspension of allenylzinc bromide (±)-1 was then allowed to warm up to r.t. and a 0.3 M etheral solution of sulfinimine (±)-2 (0.66 to 0.16 equiv) was immediately added. After 18 h stirring at r.t., the solution was quenched with a 30% aq NH₃/sat. aq NH₄Cl, a 1:2 solution. The layers were separated and the aqueous one was extracted with Et₂O (3×). The combined organic layers were washed with H₂O and brine, dried over anhyd Na₂SO₄ and concentrated in vacuo. The residual brownish oil was purified by flash chromatography over silica gel to give the corresponding diastereomerically pure trans-ethynyl N-sulfinylaziridine (±)-3.

15

CCDC 230643 contains the supplementary crystallographic data for compound (±)-3g. These data can be obtained free of charge via www.ccdc.ac.uk/conts/retrieving.html [or from Cambridge Cystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax:[phone]; or [e-mail]].

16

In the case of N-sulfonylimines, for which low selectivities are obtained (see ref. 10a), such a coordination of the zinc by the sulfonyl group has not been envisaged because of weak Lewis basicity of both nitrogen and oxygen atoms.