Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp3)–H bond functionalization reactions DOI Creative Commons

Andrés García‐Viada,

Juan C. Carretero, Javier Adrio

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an overview of the research advaces in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp 3 )–H bond functionalization reactions; including design principles, mechanistic discussions, along with potential applications limitations.

Language: Английский

Mechanistic Insights into Ru–S Complex-Catalyzed C–H Silylation and Borylation of N-Heteroarene: Distinct Bonding Interactions DOI Creative Commons

Naphol Witayapaisitsan,

Thanapat Worakul, Panida Surawatanawong

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

The silylation and borylation of N-heteroarenes are essential processes for preparing key building blocks in organic synthesis. Ru–S complex 1, [(PEt3)Ru(DmpS)]+ (DmpS = 2,6-dimesitylphenyl thiolate), catalyzes both C–H N-heteroarenes. Herein, we performed a density functional study to investigate the mechanisms 1 catalyzed 1-methylindole using hydrosilanes dialkoxyhydroborane (HBpin) dialkylhydroborane (9BBN). mechanism involves four main steps: (i) Si–H/B–H activation, (ii) silyl/boryl transfer 1-methylindole, (iii) proton abstraction yield silylated/borylated product, (iv) H2 elimination regenerate 1. rate-determining step is transfer. Notably, upon B–H bond HBpin fully cleaved, while 9BBN remains partially intact. Moreover, instead forming silylium/borenium ions, Si–H activations lead distinct Si–H/B–H-activated complexes: thiosilane/thioborane-supported Ru–H complexes hydrosilane three-center two-electron Ru–H–B 9BBN. Differences bonding interactions affect energy barriers Insights into these electronic structures provide foundation designing metal–ligand cooperative catalysts

Language: Английский

Citations

0
Ir-Catalyzed, Nitrogen-Directed C(sp3)–H and C(sp2)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand DOI Creative Commons

Tomonori Inoue,

Yu Sato, Yuki Nagashima

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4061 - 4068

Published: Feb. 21, 2025

Language: Английский

Citations

0
Methane Beryllation Catalyzed by a Base Metal Complex DOI Creative Commons
Josef T. Boronski, Agamemnon E. Crumpton, Job J. C. Struijs

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C–H bond strength this hydrocarbon. Here, using quantities (10 mol %) CpMn(CO)3 or Cp*Re(CO)3, conversion benzene bonds C–Be H–Be by CpBeBeCp has been achieved under photochemical conditions. Possible intermediates in beryllation reactions─trans-bis(beryllyl)-manganese -rhenium complexes─were also isolated. Quantum chemical calculations indicate that inherent properties beryllyl ligands─which are powerfully σ-donating feature highly Lewis acidic beryllium centers─are decisive enabling these systems.

Language: Английский

Citations

0
Unlocking redox-active reactivity of dearomatized pyridines with photochemistry toward meta-C–H functionalization of pyridines DOI

Mingkai Yang,

Mei Wang,

Haiman Zhang

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101326 - 101326

Published: March 1, 2025

Language: Английский

Citations

0
Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp3)–H bond functionalization reactions DOI Creative Commons

Andrés García‐Viada,

Juan C. Carretero, Javier Adrio

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an overview of the research advaces in Ni-, Cu-, Fe- and Co-catalyzed directed C(sp 3 )–H bond functionalization reactions; including design principles, mechanistic discussions, along with potential applications limitations.

Language: Английский

Citations

0