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

Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform Chen, Wei W. Pipaon Fernández, Nahiane Díaz Baranda, Marta Cunillera, Anton Rodríguez González, Laura Shafir, Alexandr Cuenca, Ana Belen Universitat Ramon Llull. IQS Enllaços químics Bor Silici 54 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. info:eu-repo/semantics/publishedVersion 2021-07-02 info:eu-repo/semantics/article 2041-6539 http://hdl.handle.net/20.500.14342/4075 http://dx.doi.org/10.1039/d1sc01741a eng Supplementary information Chemical Science https://www.rsc.org/suppdata/d1/sc/d1sc01741a/d1sc01741a1.pdf info:eu-repo/grantAgreement/MINECO/PN I+D/CTQ2017-85378-R info:eu-repo/grantAgreement/MICINN/PN I+D/PID2020-113661GB-I00 info:eu-repo/grantAgreement/SUR del DEC/SGR/2017 SGR 01051 info:eu-repo/grantAgreement/SUR del DEC/SGR/2017 SGR 00294 info:eu-repo/grantAgreement/URL/Projectes recerca PDI/2019-URL_Proj-034 info:eu-repo/grantAgreement/URL i La Caixa/Projectes recerca PDI/2017-URL-Intermac-010 © L'autor/a Attribution-NonCommercial 4.0 International http://creativecommons.org/licenses/by-nc/4.0/ info:eu-repo/semantics/openAccess info:eu-repo/semantics/openAccess info:eu-repo/semantics/openAccess 8 p. Royal Society of Chemistry