2026-04-18T07:57:02Zhttps://recercat.cat/oai/request

oai:recercat.cat:20.500.14342/40752025-05-28T23:43:29Zcom_2072_482405com_2072_183628col_2072_482414

00925njm 22002777a 4500 dc Chen, Wei W. author Pipaon Fernández, Nahiane author Díaz Baranda, Marta author Cunillera, Anton author Rodríguez González, Laura author Shafir, Alexandr author Cuenca, Ana Belen author 2021-07-02 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. 2041-6539 http://hdl.handle.net/20.500.14342/4075 http://dx.doi.org/10.1039/d1sc01741a Enllaços químics Bor Silici Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform