Exploring benzylic <i>gem</i>-C(sp<sup>3</sup>)–boron–silicon and boron–tin centers as a synthetic platform

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

doi:10.1039/d1sc01741a

Cited by 10 publications

(4 citation statements)

References 48 publications

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“…The last illustration involves electron rich homo‐ and heteroleptic gem ‐disilanes, which we surmised could undergo oxidative functionalization, though tetraalkylsilanes (including benzyltrialkylsilanes) are generally considered unreactive towards common oxidants (Scheme 4C) [23] . Inspired by a recent report from Shafir and Cuenca, [24] we reacted 13 ac and 13 c 2 with TMSOTf‐activated PhI(OAc) 2 at low temperature and obtained the new α‐silylated benzylacetamides 34 and 35 that still contain a potentially reactive C−Si bond in 53 % and 54 % yield respectively. In the case of 13 ac , the C−SiMe 3 bond was preferentially cleaved over the C−SiEt 3 , though the latter was not deemed oxidatively unbreakable ( 13 a→36 ).…”

Section: Resultsmentioning

confidence: 99%

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Neil,

Saadi,

Fensterbank

et al. 2023

Angew Chem Int Ed

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Benzylsilanes have found increasing applications in organic synthesis as bench-stable synthetic intermediates, yet are mostly produced by stoichiometric procedures. Catalytic alternatives based on the atomeconomical silylation of benzylic C(sp 3 )À H bonds remain scarcely available as specialized directing groups and catalytic systems are needed to outcompete the kinetically-favored silylation of C(sp 2 )À H bonds. Herein, we describe the first general and catalytic-in-metal undirected silylation of benzylic C(sp 3 )À H bonds under ambient, transition metal-free conditions using stable tert-butyl-substituted silyldiazenes (tBuÀ N=NÀ SiR 3 ) as silicon source. The high activity and selectivity of the catalytic system, exemplified by the preparation of various mono-or gem-bis benzyl(di)silanes, originates from the facile generation of organopotassium reagents, including tert-butylpotassium.

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Section: Resultsmentioning

confidence: 99%

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Neil,

Saadi,

Fensterbank

et al. 2023

Angew Chem Int Ed

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“…The other side of the coin is that secondary organoboronates are rather feeble partners for cross-coupling reactions what tends to limit the scope of the second functionalization step, which in addition is rarely performed in one-pot procedures. Solutions here might come from α-boryl silicon [32,33] or germanium [34] linchpins, for which the stereoselective cross-coupling chemistry of the secondary organosilanes and organogermanes needs to be developed. gem-Dizinc linchpins could also offer further options, but the challenge here remains to develop truly broad and efficient access to the starting linchpins.…”

Section: Discussionmentioning

confidence: 99%

Stereoselective Double Functionalization of Geminated C(sp³)‐Organodimetallic Linchpins

Banchini,

Leroux,

Le Gall

et al. 2023

ChemCatChem

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Geminated C(sp3)‐organodimetallics can serve as dinucleophilic linchpins for the rapid assembly of complex molecular structures through two consecutive electrophilic substitution reactions with two different electrophiles. Implementation of these double functionalization sequences in a stereoselective manner to develop tools for asymmetric synthesis has attracted considerable interest from the synthetic community over the last decade. The focus has been put mostly on 1,1‐bimetallic reagents containing boron, zinc or zirconium, and different strategies have been applied for such a purpose, including the diastereoselective transformation of enantioenriched chiral reagents or the enantioselective conversion of achiral or racemic derivatives. Asymmetric catalysis is at stake in most of the approaches developed. In this review article, we highlight the key advances in the development of 1,1‐bimetallic linchpins as tools for asymmetric synthesis, emphasizing the underlying general concepts.

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“…Shafir and Cuenca continued the study with gem-α,αdimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent with PhI(OAc) 2 to undergo parabenzylation reaction assisted by TMSOTf. [35] The proposed mechanism was based on "iodane-guided" [3,3]-sigmatropic rearrangement for selective coupling at the ArÀ I para CÀ H site. This reaction is suggested a [5,5]-sigmatropic rearrangement driven by hypervalent iodine.…”

Section: Para-selective Benzyl Migration With Hirsmentioning

confidence: 99%

Synthesis of Versatile Aryliodine Synthons by Aryliodonium Rearrangement Reactions

Pan,

Wang,

Han

2024

Asian J Org Chem

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The excellent reactivity of diaryliodonium salts has primarily been attributed to the efficient departure of the iodoarene unit, facilitating a variety of arylation reactions. However, one equivalent of iodoarene as a side‐product is a chemical waste in these reactions, which was criticized by chemists for hindering its popularity. Recently, the development of synthetic methodology that preserve the aryl iodine moiety received increasing attention. Oxidative rearrangement reactions involving aryliodonium reagents have significantly addressed the atom‐economic issue, thereby broadening the reaction scope. The resulting intricate aryliodine products are viewed as valuable synthons for the synthesis of natural products, pharmaceutical intermediates and other fine chemicals.

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Exploring benzylic gem-C(sp³)–boron–silicon and boron–tin centers as a synthetic platform

Abstract: 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...

Cited by 10 publications

References 48 publications

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Stereoselective Double Functionalization of Geminated C(sp³)‐Organodimetallic Linchpins

Synthesis of Versatile Aryliodine Synthons by Aryliodonium Rearrangement Reactions

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Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

Abstract: 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...

Cited by 10 publications

References 48 publications

Organopotassium‐Catalyzed Silylation of Benzylic C(sp3)−H Bonds

Organopotassium‐Catalyzed Silylation of Benzylic C(sp3)−H Bonds

Stereoselective Double Functionalization of Geminated C(sp3)‐Organodimetallic Linchpins

Synthesis of Versatile Aryliodine Synthons by Aryliodonium Rearrangement Reactions

Contact Info

Product

Resources

About

Exploring benzylic gem-C(sp³)–boron–silicon and boron–tin centers as a synthetic platform

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Organopotassium‐Catalyzed Silylation of Benzylic C(sp³)−H Bonds

Stereoselective Double Functionalization of Geminated C(sp³)‐Organodimetallic Linchpins