Pincer-Cobalt Boosts Divergenet Alkene Carbonylation under Tandem Electro-Thermo-Catalysis

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

Catalytic multicomponent carbonylation reactions with high regio- and chemoselectivity represent one of the long-pursued goals in C1 chemistry. We herein disclose a practical cobalt-catalyzed divergent radical alkene carbonylative functionalization under 1 atm CO at 23°C. The leverage tridentate NNN-type pincer ligand is key to avoid formation catalytically inert Co⁰(CO)_n species overcome occurrence oxidative organozincs, selectively tuning catalytic reactivity cobalt center for dictating full four-component carbonylation. Moreover, direct use CO₂ as source couplings can be achieved tandem electro-thermo-catalysis, thus allowing us rapidly reliably construct unsymmetric ketones ample scope excellent functional group compatibility. Remarkably, our protocol encompasses broader polyhaloalkanes electrophiles, which underwent radical-relay completely chemoselective fashion. Finally, facile modifications drug-like molecules demonstrate synthetic utility this method.

Language: Английский

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1,2-Silylpyridylation Reaction of Aryl Alkenes with Silylboronate

Organic Letters, Journal Year: 2022, Volume and Issue: 24(31), P. 5698 - 5703

Published: July 29, 2022

A metal-free silyl-pyridylation of alkenes using silyl boronates and B2pin2 through a pyridine-mediated B-interelement activation has been demonstrated, which provides practical strategy for variety C4-silylalkylated pyridines. DFT calculations control experiments show that the reaction proceeds radical addition/radical-radical coupling sequence. This protocol features broad substrate scope excellent functional group compatibility, thus it showcases great potential in late-stage modification bioactive molecules.

Language: Английский

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Intermolecular Carbosilylation of α‐Olefins with C(sp³)−C(sp) Bond Formation Involving Silylium‐Ion Regeneration

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 28, 2022

A regioselective addition of alkynylsilanes across unactivated, terminal alkenes is reported. The reaction initiated by the capture a sterically unhindered silylium ion silylated phenylacetylene derivative to form bis(silylated) ketene-like carbocation. This in situ-generated key intermediate actual catalyst that maintains catalytic cycle series electrophilic reactions ions and β-silicon-stabilized carbocations. computed mechanism fully consistent with experimental findings. unprecedented two-component carbosilylation establishes C(sp

Language: Английский

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Rare-Earth Metal Complexes Supported by 1,3-Functionalized Indolyl-Based Ligands for Efficient Hydrosilylation of Alkenes

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 62(1), P. 381 - 391

Published: Dec. 28, 2022

Two different 1,3-functionalized indolyl-based proligands 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H5N (HL1) and 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H5N (HL2) were designed, prepared in high yields, successfully applied to rare-earth metal chemistry showing reactivities bondings with the central metals. The reactions of HL1 RE(CH2SiMe3)3(THF)2 provided two types complexes: pincer type mononuclear complexes κ3-(L1)RE(CH2SiMe3)2 [L1 = 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H4N, RE Lu(1), Yb(2)], dinuclear alkyl (per alkyl/per metal) having ligand novel coordination modes {(η1:(μ-η2:η1):η1-1-(2-C4H7O)CH2-3-[2-tBuC6H5NCH-(CH2SiMe3)]C8H4N)RECH2SiMe3}2 [RE Er(3), Y(4), Dy(5), Gd(6)]. Meanwhile, HL2 led isolation characterization only dialkyl κ3-(L2)RE(CH2SiMe3)2 [L2 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N, Lu(7), Gd(8)] bearing chelate form. formed through sp2 C–H activation 2-indolyl moiety, while produced unexpectedly tandem C═N insertion into RE–CH2SiMe3 bond. These fully characterized by spectroscopic methods, elemental analyses, single-crystal X-ray crystallography. applications synthesized as catalysts for hydrosilylation terminal alkenes phenylsilane are described. Anti-Markovnikov addition products aliphatic olefins, Markovnikov isolated aromatic olefins selectivity absence cocatalysts. It is found that exhibited best catalytic activity advantages mild reaction conditions, short time, low catalyst loading, wide substrate applicability comparison reported catalysts.

Language: Английский

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Application of Solid Me₃SiZnI for the Synthesis of Aryl and Alkyl Trimethylsilanes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1442 - 1447

Published: Jan. 24, 2024

Abstract Silylzinc reagents are desirable for the synthesis of organosilanes due to their compatibility with functional groups; however, use pyrophoric silyllithium and dissolved lithium salts in production hinders development. Our solid Me 3 SiZnI circumvents these limitations, herein, we demonstrate its significance aryl alkyl trimethylsilanes via cross‐coupling bromides. The milder reaction condition tolerates groups such as MOM, Boc, Bpin, aldehydes.

Language: Английский

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