75447-85-7Relevant academic research and scientific papers
Exploring benzylicgem-C(sp3)-boron-silicon and boron-tin centers as a synthetic platform
Baranda, Marta Díaz,Chen, Wei W.,Cuenca, Ana B.,Cunillera, Anton,Fernández, Nahiane Pipaon,Rodríguez, Laura G.,Shafir, Alexandr
, p. 10514 - 10521 (2021)
A stepwise build-up of multi-substituted Csp3carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes howgem-α,α-dimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent sets are an excellent stepping stone towards diverse substitution patterns. Thesegem-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 formedgem-Csp3centers 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 suchgem-dimetalloidsviathe iodane-guided C-H coupling approach. DFT calculations show that this transfer of the (α-Bpin)benzyl group proceedsviaunusual [5,5]-sigmatropic rearrangement and is driven by the high-energy iodine(iii) center. As a complementary tool, thegem-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 reactivegem-α,α-silyl/BF3K building blocks.
BASE CLEAVAGE OF SUBSTITUTED - AND -TRIMETHYLSILANE. STABILIZATION OF CARBANIONIC CENTRES BY 2-THIENYL AND 2-FURYL GROUPS
Eaborn, Colin,Pirazzini, Graziella,Seconi, Giancarlo,Ricci, Alfredo
, p. 339 - 346 (2007/10/02)
Rates of cleavage by NaOMe-MeOH at 25 deg C have been determined for (2-thienyl)2CHSiMe3 and for the compounds Ph(2-thienyl)CHSiMe3 and Ph(2-furyl)CHSiMe3 and some of their derivatives with a substituent in the m- or p-position of the phenyl group or the
