Well‐defined Cp*Co(III)‐catalyzed Hydrogenation of Carbonates and Polycarbonates DOI

Pardeep Dahiya,

Manoj Kumar Gangwar, Basker Sundararaju

et al.

ChemCatChem, Journal Year: 2020, Volume and Issue: 13(3), P. 934 - 939

Published: Nov. 19, 2020

Abstract We herein report the catalytic hydrogenation of carbonates and polycarbonates into their corresponding diols/alcohols using well‐defined, air‐stable, high‐valent cobalt complexes. Several novel Cp*Co(III) complexes bearing N , O ‐chelation were isolated for first time structurally characterized by various spectroscopic techniques including single crystal X‐ray crystallography. These Co(III) have shown excellent activity to produce value added from carbonate through molecular hydrogen as sole reductant or i PrOH transfer source. To demonstrate developed methodology's practical applicability, we recycled bisphenol A monomer compact disc (CD) under established reaction conditions phosphine‐free, earth‐abundant, air‐ moisture‐stable catalysts.

Language: Английский

Borrowing Hydrogen for Organic Synthesis DOI Creative Commons

Benjamin G. Reed‐Berendt,

Daniel E. Latham,

Mubarak B. Dambatta

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 570 - 585

Published: March 25, 2021

Borrowing hydrogen is a process that used to diversify the synthetic utility of commodity alcohols. A catalyst first oxidizes an alcohol by removing form reactive carbonyl compound. This intermediate can undergo diverse range subsequent transformations before returns "borrowed" liberate product and regenerate catalyst. In this way, alcohols may be as alkylating agents whereby sole byproduct one-pot reaction water. recent decades, significant advances have been made in area, demonstrating many effective methods access valuable products. outlook highlights diversity metal biocatalysts are available for approach, well various performed, focusing on selection most advances. By succinctly describing conveying versatility borrowing chemistry, we anticipate its uptake will increase across wider scientific audience, expanding opportunities further development.

Language: Английский

Citations

321
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
Control of Absolute Stereochemistry in Transition‐Metal‐Catalysed Hydrogen‐Borrowing Reactions DOI Creative Commons
Timothy Kwok,

Oskar Hoff,

Roly J. Armstrong

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(57), P. 12912 - 12926

Published: April 16, 2020

Abstract Hydrogen‐borrowing catalysis represents a powerful method for the alkylation of amine or enolate nucleophiles with non‐activated alcohols. This approach relies upon catalyst that can mediate strategic series redox events, enabling formation C−C and C−N bonds producing water as sole by‐product. In majority cases these reactions have been employed to target achiral racemic products. contrast, focus this Minireview is hydrogen‐borrowing‐catalysed in which absolute stereochemical outcome process be controlled. Asymmetric hydrogen‐borrowing rapidly emerging synthesis enantioenriched carbonyl containing products examples involving both bond are presented. A variety different approaches discussed including use chiral auxiliaries, asymmetric enantiospecific processes.

Language: Английский

Citations

100
Chromium‐Catalyzed Alkylation of Amines by Alcohols DOI Creative Commons
Fabian Kallmeier, Robin Fertig, Τ. Irrgang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(29), P. 11789 - 11793

Published: March 18, 2020

Abstract The alkylation of amines by alcohols is a broadly applicable, sustainable, and selective method for the synthesis alkyl amines, which are important bulk fine chemicals, pharmaceuticals, agrochemicals. We show that Cr complexes can catalyze this C−N bond formation reaction. synthesized isolated 35 examples alkylated including 13 previously undisclosed products, use amino as alkylating agents was demonstrated. catalyst tolerates numerous functional groups, hydrogenation‐sensitive examples. Compared to many other alcohol‐based amine methods, where stoichiometric amount base required, our Cr‐based system gives yields higher than 90 % various with catalytic base. Our study indicates borrowing hydrogen or autotransfer reactions could thus be an alternative Fe, Co, Mn, noble metals in (de)hydrogenation catalysis.

Language: Английский

Citations

91
Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect DOI
Ishani Borthakur,

Anirban Sau,

Sabuj Kundu

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

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
Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis DOI

Feixiang Sun,

Jiamin Huang,

Zhihong Wei

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 21, 2023

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis γ-disubstituted and β-disubstituted ketones is reported. Employing well-defined Mn-MACHOPh as catalyst, this novel protocol has a broad substrate scope with good functional group tolerance affords diverse library valuable disubstituted in moderate to yields. The strong influence reaction temperature on selective formation alcohol products was theorized preliminary DFT studies. Studies have shown that Gibbs free energy thermodynamically more favourable than corresponding at lower temperature.

Language: Английский

Citations

31
Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds DOI
Sourajit Bera, Lalit Mohan Kabadwal, Debasis Banerjee

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

Citations

17
Manganese complex-catalysed α-alkylation of ketones with secondary alcohols enables the synthesis of β-branched carbonyl compounds DOI Open Access
Satyadeep Waiba, Sayan K. Jana, Ayan Jati

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(60), P. 8376 - 8379

Published: Jan. 1, 2020

Herein, β-branched carbonyl compounds were synthesised via the α-alkylation of ketones with secondary alcohols under "borrowing hydrogen" catalysis. A wide range alcohols, including various cyclic, acyclic, symmetrical, and unsymmetrical have been successfully applied developed reaction conditions. manganese(i) complex bearing a phosphine-free multifunctional ligand catalysed produced water as sole byproduct.

Language: Английский

Citations

58