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. 2017 Nov 27;9(4):904-909.
doi: 10.1039/c7sc04351a. eCollection 2018 Jan 28.

Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles

Surendra Thapa  1 , Roshan K Dhungana  1 , Rajani Thapa Magar  1 , Bijay Shrestha  1 , Shekhar Kc  1 , Ramesh Giri  1
Affiliations

Ni-catalysed regioselective 1,2-diarylation of unactivated olefins by stabilizing Heck intermediates as pyridylsilyl-coordinated transient metallacycles

Surendra Thapa et al. Chem Sci. .

Abstract

We report a Ni-catalysed diarylation of unactivated olefins in dimethylpyridylvinylsilane by intercepting Heck C(sp3)-NiX intermediates, derived from aryl halides, with arylzinc reagents. This approach utilizes a modifiable pyridylsilyl moiety as a coordinating group that plays a dual role of intercepting oxidative addition species to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination, and facilitate transmetalation/reductive elimination. This method affords 1,2-diarylethylsilanes, which can be readily oxidized to 1,2-diarylethanols that occur as structural motifs in 3-aryl-3,4-dihydroisocoumarin and dihydrostilbenoid natural products.

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Figures

Scheme 1
Scheme 1. Two well-known transformations working as side reactions during regioselective olefin diarylation.
Scheme 2
Scheme 2. Strategy for olefin dicarbofunctionalization.
Scheme 3
Scheme 3. Transformation of silyl group to alcohol.
Scheme 4
Scheme 4. Establishing the role of pyridylsilyl group.
Scheme 5
Scheme 5. Radical clock experiment.
Scheme 6
Scheme 6. Proposed catalytic cycle.
See this image and copyright information in PMC

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