Issue 31, 2021

Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

Abstract

A stepwise build-up of multi-substituted Csp3 carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how gem-α,α-dimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent sets are an excellent stepping stone towards diverse substitution patterns. These gem-dimetalloids were readily accessed, either by known carbenoid insertion into C–B bonds or by the newly developed scalable deprotonation/metallation approach. Highly chemoselective transformations of either the C–Si (or C–Sn) or the C–B bonds in the newly formed gem-Csp3 centers have been achieved through a set of approaches, with a particular focus on exploiting the synthetically versatile polarity reversal in organometalloids by λ3-aryliodanes. Of particular note is the metal-free arylation of the C–Si (or C–Sn) bonds in such gem-dimetalloids via the iodane-guided C–H coupling approach. DFT calculations show that this transfer of the (α-Bpin)benzyl group proceeds via unusual [5,5]-sigmatropic rearrangement and is driven by the high-energy iodine(III) center. As a complementary tool, the gem-dimetalloid C–B bond is shown to undergo a potent and chemoselective Suzuki–Miyaura arylation with diverse Ar–Cl, thanks to the development of the reactive gem-α,α-silyl/BF3K building blocks.

Graphical abstract: Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

Supplementary files

Article information

Article type
Edge Article
Submitted
27 3月 2021
Accepted
28 6月 2021
First published
02 7月 2021
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., 2021,12, 10514-10521

Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

W. W. Chen, N. P. Fernández, M. D. Baranda, A. Cunillera, L. G. Rodríguez, A. Shafir and A. B. Cuenca, Chem. Sci., 2021, 12, 10514 DOI: 10.1039/D1SC01741A

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