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Synthesis 2022; 54(19): 4361-4370
DOI: 10.1055/s-0040-1719925
paper

Stereoselective Conjugate Addition-Enamination of α-Linear N-tert-Butanesulfinyl Ketimines with Nitroolefins

Nuermaimaiti Yisimayili
a   State Key Laboratory Basis of Xinjiang Indigenous Medicinal Plants Resource Utilization, and Key Laboratory of Plants Resources and Chemistry of Arid Zone, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, P. R. of China
c   University of Chinese Academy of Sciences, Beijing 100039, P. R. of China
,
Li-Feng Chu
b   School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. of China
,
Jie Feng
a   State Key Laboratory Basis of Xinjiang Indigenous Medicinal Plants Resource Utilization, and Key Laboratory of Plants Resources and Chemistry of Arid Zone, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, P. R. of China
c   University of Chinese Academy of Sciences, Beijing 100039, P. R. of China
,
Chong-Dao Lu∗
a   State Key Laboratory Basis of Xinjiang Indigenous Medicinal Plants Resource Utilization, and Key Laboratory of Plants Resources and Chemistry of Arid Zone, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, P. R. of China
b   School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. of China
› Author AffiliationsThis work was supported by the National Natural Science Foundation of China (22161048, 21871292) and Yunnan University.
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Abstract

N-Sulfinyl metalloenamines, generated by deprotonating α-linear N-tert-butanesulfinyl ketimines, reacted with nitroalkenes via stereoselective conjugate addition to give Michael adducts with opposite stereochemistry to that obtained using α-branched sulfinylketimines. In the presence of excess base (2.5 equiv t-BuOK), the adducts derived from α-linear ketimines were further stereoselectively deprotonated to afford the corresponding kinetically favorable N-sulfinyl (Z)-enamine derivatives in good yields with good stereoselectivities. A reaction model was proposed to rationalize the observed stereochemistry.

Key words

N-sulfinyl metalloenamines - conjugate addition - deprotonation - enamination - stereoselectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1719925.
  • Supporting Information


Publication History

Received: 02 April 2022

Accepted after revision: 12 April 2022

Article published online:
23 May 2022

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