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. 2018 May 16;9(23):5278-5283.
doi: 10.1039/c8sc01735b. eCollection 2018 Jun 21.

Directed nickel-catalyzed 1,2-dialkylation of alkenyl carbonyl compounds

Joseph Derosa  1 , Vincent A van der Puyl  1 , Van T Tran  1 , Mingyu Liu  1 , Keary M Engle  1
Affiliations

Directed nickel-catalyzed 1,2-dialkylation of alkenyl carbonyl compounds

Joseph Derosa et al. Chem Sci. .

Abstract

A nickel-catalyzed conjunctive cross-coupling of non-conjugated alkenes, alkyl halides, and alkylzinc reagents is reported. Regioselectivity is controlled by chelation of a removable bidentate 8-aminoquinoline directing group. Under optimized conditions, a wide range of 1,2-dialkylated products can be accessed in moderate to excellent yields. To the best of our knowledge, this report represents the first example of three-component 1,2-dialkylation of non-conjugated alkenes to introduce differentiated alkyl fragments.

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Figures

Scheme 1
Scheme 1. Three-component 1,2-dicarbofunctionalization with C(sp3) reaction partners: precedents and current work.
Scheme 2
Scheme 2. Removal of the AQ directing group.
Scheme 3
Scheme 3. Mechanistic experiment involving (bromomethyl)cyclopropane as an electrophile.
Scheme 4
Scheme 4. Proposed catalytic cycle.
See this image and copyright information in PMC

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