Exploring benzylic gem-C(sp(3))-boron-silicon and boron-tin centers as a synthetic platform

Wei W. Chen, Nahiane Pipaon Fernández, Marta Díaz Baranda, Anton Cunillera, Laura G. Rodríguez, Alexandr Shafir, Ana B. Cuenca

Research output: Indexed journal article Articlepeer-review

8 Citations (Scopus)

Abstract

A stepwise build-up of multi-substituted C(sp)TJ0VL(3)X carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how gem-alpha,alpha-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-C-sp (3) centers have been achieved through a set of approaches, with a particular focus on exploiting the synthetically versatile polarity reversal in organometalloids by lambda(3)-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 (alpha-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-alpha,alpha-silyl/BF3K building blocks.
Original languageEnglish
Pages (from-to)10514-10521
Number of pages8
JournalChemical Science
Volume12
Issue number31
Early online dateJul 2021
DOIs
Publication statusPublished - 21 Aug 2021

Keywords

  • Cross-coupling reactions
  • Esters
  • 1,1-diborylalkanes
  • Substitution
  • Generation
  • Reactivity

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