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

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

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NNN manganese complex-catalyzed α-alkylation of methyl ketones using alcohols: an experimental and computational study

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(7), P. 3236 - 3243

Published: Jan. 1, 2024

A quinoline-based pincer Mn catalyst for α-alkylation of methyl ketones using primary alcohols as alkyl surrogates is presented. The C–C bond formation reaction proceeds via a hydrogen auto-transfer protocol, generating water the only by-product.

Language: Английский

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[(PPh₃)₂NiCl₂]-Catalyzed C–N Bond Formation Reaction via Borrowing Hydrogen Strategy: Access to Diverse Secondary Amines and Quinolines

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(9), P. 6994 - 7001

Published: April 27, 2021

Commercially available [(PPh3)2NiCl2] was found to be an efficient catalyst for the mono-N-alkylation of (hetero)aromatic amines, employing alcohols deliver diverse secondary including drug intermediates chloropyramine (5b) and mepyramine (5c), in excellent yields (up 97%) via borrowing hydrogen strategy. This method shows a superior activity (TON up 10000) with broad substrate scope at low loading 1 mol % short reaction time. Further, this strategy is also successful accessing various quinoline derivatives following acceptorless dehydrogenation pathway.

Language: Английский

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Nickel catalyzed sustainable synthesis of benzazoles and purines via acceptorless dehydrogenative coupling and borrowing hydrogen approach

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(33), P. 7217 - 7233

Published: Jan. 1, 2021

Herein we report nickel-catalyzed sustainable synthesis of a few chosen five-membered fused nitrogen heterocycles such as benzimidazole, purine, benzothiazole, and benzoxazole via acceptorless dehydrogenative functionalization alcohols. Using bench stable, easy to prepare, inexpensive Ni(ii)-catalyst, [Ni(MeTAA)] (1a), featuring tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)), wide variety polysubstituted derivatives were prepared coupling alcohols with 1,2-diaminobenzene, 4,5-diaminopyrimidine, 2-aminothiphenol, 2-aminophenol, respectively. A array benzimidazoles also borrowing hydrogen approach involving donors 2-nitroanilines acceptors. control experiments performed understand the reaction mechanism.

Language: Английский

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Electronically tuneable orthometalated Ru^II–NHC complexes as efficient catalysts for C–C and C–N bond formations via borrowing hydrogen strategy

Catalysis Science & Technology, Journal Year: 2021, Volume and Issue: 12(1), P. 67 - 74

Published: Nov. 10, 2021

A series of simple and electronically tuneable cyclometalated Ru II –NHC complexes have been explored as efficient catalysts for various C–C/N bond forming reactions via a BH methodology.

Language: Английский

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Nickel-Catalyzed Deoxygenative Amidation of Alcohols with Carbamoyl Chlorides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2297 - 2302

Published: March 11, 2024

We report a deoxygenative amidation reaction of alcohols with carbamoyl chlorides to afford amides through nickel–photoredox dual catalysis. Good excellent yields can be obtained even for diverse complex sugar and steroid derivatives. The is scalable, the synthetic utility was demonstrated by homologation deliver several important γ-amino synthetically challenging bioactive compound intermediate.

Language: Английский

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Phosphine‐Free NNN‐Manganese(II) Catalyzed C‐alkylation of Methyl N‐Heteroarenes via Borrowing Hydrogen

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1531 - 1537

Published: Jan. 31, 2024

Abstract Mn(II)‐catalyzed alkylations of methyl N ‐heteroarenes was reported via borrowing hydrogen strategy with alcohols as the alkylating reagent. The developed geometry‐constrained benzimidazole‐iminopyridyl ligand played a key role in promoting transformation and stablizing metal center. A wide range (aromatic, heteroaromatic aliphatic) ‐Heteroarenes could be able to apply current catalytic system, TON up 7400.

Language: Английский

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Selective Monoalkylation or Dialkylation of Indenes with Alcohols by Bis-N-Heterocyclic Carbene Manganese

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18032 - 18044

Published: Nov. 22, 2024

Selective direct alkylation of indenes is important for the synthesis and decoration indene derivatives. In contrast to traditional methods, using unactivated alcohol as reagents via borrowing hydrogen or autotransfer highly attractive. However, nature high-lying lowest unoccupied molecular orbital condensation intermediate raises a big challenge development BH system alcohols. Through tuning stability reactivity metal-hydride species by theoretical prediction, herein, we succeeded in developing non-noble Mn-catalyzed selective monoalkylation dialkylation under mild conditions, producing corresponding versatile alkylated satisfactory yields. A broad scope substrates including primary benzylic, aliphatic, amino, hydroxyl, second alcohols well various are tolerated system. Additionally, this method could be used potential precatalyst complexes bioactive molecules. Mechanistic studies control experiments, kinetic investigations, isotope effect, deuterium labeling density functional theory calculations, reveal proper successful process.

Language: Английский

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Ru^II-Complexes of heteroditopic chelating NHC ligands: effective catalysts for the β-alkylation of secondary alcohols and the synthesis of 2-alkylaminoquinoline derivatives following the dehydrogenative protocol

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(9), P. 1945 - 1951

Published: Jan. 1, 2022

Ru II -Complexes of a heteroditopic NHC ligand, featuring ImNHC and tzNHC donors, were noted to be very efficient catalysts (up 0.001 mol%) for β-alkylation secondary alcohols one pot synthesis diverse 2-alkylaminoquinoline derivatives.

Language: Английский

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N-Heterocyclic Carbene-Supported Nickel-Catalyzed Selective (Un)Symmetrical N-Alkylation of Aromatic Diamines with Alcohols

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(2), P. 1135 - 1146

Published: Jan. 5, 2023

The "borrowing hydrogen" (BH) approach for the N-alkylation of phenylenediamines using alcohols as coupling partners is highly challenging due to selectivity issue generated products. Furthermore, development base-metal systems that can potentially substitute precious metals with competitive activity a major challenge in BH catalysis. We present herein an efficient protocol N,N'-di-alkylation aromatic diamines situ-generated Ni-NHC complex from NiCl2 and ligand L1, which gave access wide range N,N'-di-alkylated orthophenylene (rather than generally observed benzimidazole derivatives), meta- para-phenylene along 2,6-diamino pyridine derivatives good excellent yields. Moreover, catalyst system was also successful derivatization clinically important drug molecule, Dapsone. Notably, could be applied effectively synthesize unsymmetrically substituted via sequential alkylation first report best our knowledge. Diverse control experiments including deuterium incorporation studies suggest proceeds sequence.

Language: Английский

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