Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform
| Autor: | Anton Cunillera, Alexandr Shafir, Ana B. Cuenca, Laura G Rodríguez, Marta Díaz Baranda, Wei W. Chen, Nahiane Pipaon Fernández |
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| Přispěvatelé: | Ministerio de Economía y Competitividad (España) |
| Rok vydání: | 2021 |
| Předmět: |
Materials science
Silicon 010405 organic chemistry Substituent chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Chemistry chemistry.chemical_compound Deprotonation chemistry Reagent Benzyl group Tin Boron Carbenoid |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/d1sc01741a |
| Popis: | 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. This work was funded by MINECO (CTQ2017-86936-P), MICINN (PID2020-113661GB-I00) and AGAUR (2017 SGR 01051 and 2017 SGR 00294), as well as financial support from URL (2019-URL_Proj-034), IQS-Obra Social La Caixa (2017-URL-Intermac-010) and an entry-level grant from CSIC. IQS is also acknowledged for a doctoral scholarship to W. W. C., and CSIC for the JAE Intro scholarship for L. R. G. |
| Databáze: | OpenAIRE |
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