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

Chemical Science Pub Date: 2017-11-27 DOI: 10.1039/C7SC04351A

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.

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