Issue 4, 2018

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Oct 2017
Accepted
26 Nov 2017
First published
27 Nov 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 904-909

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

S. Thapa, R. K. Dhungana, R. T. Magar, B. Shrestha, S. KC and R. Giri, Chem. Sci., 2018, 9, 904 DOI: 10.1039/C7SC04351A

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