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. 2022 Jun 17;12(12):7262-7268.
doi: 10.1021/acscatal.2c01697. Epub 2022 Jun 2.

Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines

Vivek Aryal  1 , Lucas J Chesley  1 , Doleshwar Niroula  1 , Rishi R Sapkota  1 , Roshan K Dhungana  1 , Ramesh Giri  1
Affiliations

Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines

Vivek Aryal et al. ACS Catal. .

Abstract

We disclose a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ-alkenylketimines with aryl halides and alkylzinc reagents. The reaction produces γ-C(sp3)-branched δ-arylketones with the construction of two new C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. Electron-deficient alkenes play crucial dual roles as ligands to stabilize reaction intermediates and to increase catalytic rates for the formation of C(sp3)-C(sp3) bonds. This alkene alkylarylation reaction is also effective for secondary alkylzinc reagents and internal alkenes, and proceeds with a complete regio- and stereocontrol, affording products with up to three contiguous all-carbon all-cis secondary stereocenters.

Keywords: C(sp3)-C(sp3); alkenes; alkylarylation; imines; nickel-catalyzed; stereoselective.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Fig. 1.
Fig. 1.
(a) Reaction profiles with and without DMFU. Inset is the initial rate. (b) Reaction profiles with alkene ligands 4-6. (c) Reaction profiles with alkene ligands 4, and 7-9. (d) Initial rates of reactions with alkene ligands 4, and 7-9.
Scheme 1.
Scheme 1.
Challenges of using C(sp3)-organometallic reagents in alkene dicarbofunctionalization reactions
Scheme 2.
Scheme 2.
Examination of electron-deficient alkenes and alkynes as ligands, and optimization of reaction parameters
Scheme 3.
Scheme 3.
Reaction scheme for kinetic studies by 19F NMR
Scheme 4.
Scheme 4.
Proposed steps for controlling relative stereochemistry of three contiguous all-cis stereocenters
See this image and copyright information in PMC

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