Highly Regio‐ and Stereoselective Hydrosilylation of Alkynes Catalyzed by Tridentate Cobalt Complexes DOI

Degong Kong,

Bowen Hu, Dafa Chen

et al.

Chemistry - An Asian Journal, Journal Year: 2019, Volume and Issue: 14(15), P. 2694 - 2703

Published: May 29, 2019

Several cobalt complexes bearing tridentate (NNN) ligands were synthesized and served as precatalysts for alkyne hydrosilylation with Ph2 SiH2 . For terminal alkynes, the catalyst L2 b-CoCl2 was selected, resulted in corresponding α-vinylsilanes high (Markovnikov) regioselectivity extensive functional-group tolerance. internal diaryl c-CoCl2 exhibited best activity, afforded E-selective vinylsilanes through syn-addition excellent yield under mild conditions.

Language: Английский

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions DOI

Adam Cook,

Stephen G. Newman

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

Citations

39

Direct Synthesis of Cycloalkanes from Diols and Secondary Alcohols or Ketones Using a Homogeneous Manganese Catalyst DOI Creative Commons
Akash Kaithal, Lisa‐Lou Gracia, Clément Camp

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(44), P. 17487 - 17492

Published: Oct. 29, 2019

A method for the synthesis of substituted cycloalkanes was developed using diols and secondary alcohols or ketones via a cascade hydrogen borrowing sequence. non-noble air-stable manganese catalyst (2 mol %) used to perform this transformation. Various 1,5-pentanediols (3-4 equiv) (1 were investigated prepare collection cyclohexanes in diastereoselective fashion. Similarly, cyclopentane, cyclohexane, cycloheptane rings constructed from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, sterically hindered following (4 + 1), (5 (6 1) strategy, respectively. This reaction provides an atom economic methodology construct two C-C bonds at single carbon center generating high-value readily available as feedstock earth-abundant metal catalyst.

Language: Английский

Citations

87

Iridium(I)-Catalyzed C–C and C–N Bond Formation Reactions via the Borrowing Hydrogen Strategy DOI
Sertaç Genç, Burcu Arslan, Süleyman Gülcemal

et al.

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(10), P. 6286 - 6297

Published: April 15, 2019

Iridium(I) complexes having an imidazol-2-ylidene ligand with benzylic wingtips efficiently catalyzed the β-alkylation of secondary alcohols primary and acceptorless dehydrogenative cyclization 2-aminobenzyl alcohol ketones through a borrowing hydrogen pathway. The β-alkylated alcohols, including cholesterol derivatives, substituted quinolines were obtained in good yields by using minute amount catalyst catalytic NaOH or KOH under air atmosphere, liberating water (and H2 case quinoline synthesis) as sole byproduct. Notably, this system demonstrated turnover numbers 940 000 (for down to 0.0001 mol % = 1 ppm catalyst) 9200 (acceptorless ketones).

Language: Английский

Citations

78

Iron-Catalyzed α-Alkylation of Ketones with Secondary Alcohols: Access to β-Disubstituted Carbonyl Compounds DOI
Léo Bettoni, Sylvain Gaillard, Jean‐Luc Renaud

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(5), P. 2064 - 2069

Published: Feb. 24, 2020

An iron-catalyzed borrowing hydrogen strategy has been applied in the synthesis of β-branched carbonyl compounds. Various secondary benzylic and aliphatic alcohols have used as alkylating reagents under mild reaction conditions. The ketones isolated good to excellent yield. Deuterium labeling experiments provide evidence that alcohol is hydride source this no reversible step or hydrogen/deuterium scrambling takes place during process.

Language: Английский

Citations

76

Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols DOI

Dipanjan Bhattacharyya,

Bikash Kumar Sarmah,

Sekhar Nandi

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 869 - 875

Published: Jan. 21, 2021

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary to α-alkylated ketones and two different β-branched are reported. Notably, this transformation is environmentally benign atom efficient H2O H2 gas as the only byproducts. The protocol extended gram-scale reaction for functionalization complex vitamin E cholesterol derivatives.

Language: Английский

Citations

58

Recent advances on cross-coupling of alcohols via borrowing hydrogen catalysis DOI

Suteerna Mullick,

Adrija Ghosh, Debasis Banerjee

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(30), P. 4002 - 4014

Published: Jan. 1, 2024

This article highlights the recent advances and significance of β-alkylation reactions towards synthesis higher order alcohols.

Language: Английский

Citations

14

Recent Advances in Homogeneous Catalysis via Metal–Ligand Cooperation Involving Aromatization and Dearomatization DOI Open Access
Takuya Shimbayashi, Ken‐ichi Fujita

Catalysts, Journal Year: 2020, Volume and Issue: 10(6), P. 635 - 635

Published: June 7, 2020

Recently, an increasing number of metal complex catalysts have been developed to achieve the activation or transformation substrates based on cooperation between atom and its ligands. In such “cooperative catalysis,” ligand not only is bound metal, where it exerts steric electronic effects, but also functionally varies structure during elementary processes catalytic reaction. this review article, we focus metal–ligand involving aromatization dearomatization ligand, thus introducing newest developments examples homogeneous reactions.

Language: Английский

Citations

61

Nickel-Catalyzed Guerbet Type Reaction: C-Alkylation of Secondary Alcohols via Double (de)Hydrogenation DOI

Reshma Babu,

Murugan Subaramanian, Siba P. Midya

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(9), P. 3320 - 3325

Published: April 21, 2021

Acceptorless double dehydrogenative cross-coupling of secondary and primary alcohols under nickel catalysis is reported. This Guerbet type reaction provides an atom- a step-economical method for the C-alkylation mild, benign conditions. A broad range substrates including aromatic, cyclic, acyclic, aliphatic was well tolerated. Interestingly, cholesterol derivatives cyclopentanol with various were also demonstrated.

Language: Английский

Citations

57

Guerbet-type β-alkylation of secondary alcohols catalyzed by chromium chloride and its corresponding NNN pincer complex DOI

Himani Narjinari,

Niharika Tanwar,

Lakshay Kathuria

et al.

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(15), P. 4753 - 4762

Published: Jan. 1, 2022

β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular is involved with a KIE 7.33 and insertion α-alkylated ketone into Cr–H bond as the RDS.

Language: Английский

Citations

34

Recent Advances for Alkylation of Ketones and Secondary Alcohols Using Alcohols in Homogeneous Catalysis DOI

Dongyuan Yang,

Hongli Wang, Chun‐Ran Chang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(18), P. 3100 - 3121

Published: July 4, 2022

Abstract The alkylation of ketones or secondary alcohols using as alkylating agents via hydrogen borrowing strategy presents a powerful method for the synthesis ɑ‐alkylated ketones. In this review, we summarize progress catalyzed by Ir, Pd, Rh, Ru, Mn, Fe, Co, Ni, and Cu catalysts α‐alkylation with cross‐coupling from 2017 to 2021. A wide range (aromatic aliphatic ketones) (benzylic primary alcohols, aromatic alkenyl diols) are well tolerated. Furthermore, also discuss current challenges propose perspectives on coming development in filed. objective present review is give an overview recent advances β‐alkylation alcohols. Finally, hope that will inspirations magnified image

Language: Английский

Citations

30