Synthesis 2022; 54(15): 3341-3350
DOI: 10.1055/s-0040-1719913
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External-Ligand-Free, Nickel-Catalyzed Alkenylation of N-Sulfonylamines with Internal Alkynes

Jia-Yue Li
a   Zhejiang University, Hangzhou 310027, Zhejiang Province, P. R. of China
b   Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, P. R. of China
,
Lun Li
b   Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, P. R. of China
,
Yun-Zhi Lin
b   Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, P. R. of China
,
Hang Shi
b   Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, P. R. of China
c   Institute of Natural Sciences, Westlake Institute for Advanced Study, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, P. R. of China
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This work was supported by the ‘Pioneer’ and ‘Leading Goose’ R & D Program of Zhejiang (2022SDXHDX0006) and the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (2020R01004).


Abstract

Allylic amines were synthesized via a nickel-catalyzed coupling reaction between various N-sulfonylamines and internal alkynes. The catalytic reaction was by-product-free and proceeded without the need for additional oxidant/reductant or activating reagent. As improvements over established methods, the present approach avoids the need for an external ligand, which increases the value of the approach with respect to atom economy, and it uses bench-stable Ni(II)Br2(dme) instead of Ni(0)(COD)2 as the source of the nickel catalyst. Mechanistic studies revealed that a catalytic amount of a strong base (i.e., KO t Bu) was essential for the formation of active Ni(0) catalyst, which, along with an imine intermediate, then initiated the catalytic cycle.

Supporting Information



Publikationsverlauf

Eingereicht: 18. Januar 2022

Angenommen nach Revision: 18. Februar 2022

Artikel online veröffentlicht:
20. April 2022

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