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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 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.

Язык: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 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.

Язык: Английский

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

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4002 - 4014

Опубликована: Янв. 1, 2024

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

Язык: Английский

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Manganese‐Catalyzed Chemoselective Coupling of Secondary Alcohols, Primary Alcohols and Methanol

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(17)

Опубликована: Фев. 27, 2023

Herein, we report a manganese-catalyzed three-component coupling of secondary alcohols, primary alcohols and methanol for the synthesis β,β-methylated/alkylated alcohols. Using our method, series 1-arylethanol, benzyl alcohol derivatives, undergo sequential efficiently to construct assembled with high chemoselectivity in moderate good yields. Mechanistic studies suggest that reaction proceeds via methylation benzylated intermediate generate final product.

Язык: Английский

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Surmounting Alkoxide Trap Strategy: N-Heterocyclic Carbene Chromium(0)-Catalyzed C-Alkylation between Alcohols

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12481 - 12493

Опубликована: Сен. 8, 2023

The crucial role of the alkoxide trap problem and impact oxidation state chromium center were demonstrated on catalytic activity due to d-wall issue. Through strategy surmounting trap, a Cr(0) catalyst was presented herein for efficient C-alkylation between alcohols via borrowing hydrogen/hydrogen autotransfer. synthesized bis-(N-heterocyclic carbene)-Cr(0) system shows an performance (40 examples, up 96% yield). Only loading cheap readily available base NaOH is effective enough reaction. Compared with Cr(III)/Cr(II), can well avoid d-p π interaction in key metal-alkoxide intermediate, thus overcoming thermodynamic sink problem. It plausible that Cr(III) systems need be reduced Cr(II) weakening effect enhancing by using reductive strong bases. This should helpful development nonprecious transition metal catalysts.

Язык: Английский

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Pincer-Cobalt-Catalyzed Guerbet-Type β-Alkylation of Alcohols in Air under Microwave Conditions

Organometallics, Год журнала: 2022, Номер 41(22), С. 3387 - 3398

Опубликована: Авг. 5, 2022

Pincer complexes of the type (R2NNN)CoCl2 (R = iPr, tBu, Cy, Ph, p-F-C6H4) derived from environmentally benign, earth-abundant, and inexpensive base metal cobalt have been synthesized that exist in equilibrium with [(R2NNN)2Co]CoCl4. Among these complexes, (iPr2NNN)CoCl2 has found to be highly efficient for catalytic β-alkylation alcohols air at 140 °C. While pincer-Co (0.0025 mol %)-catalyzed presence NaOtBu (2.5 %) took 24 h (85%, 34000 TON 1417 TO/h) under conventional heating (140 °C), corresponding reaction microwave conditions °C 75 W) was complete only 2 comparable yields (83%, 33200 TON), albeit a better TOF (16600 TO/h). In contrast, CoCl2 otherwise identical leads lower both (66%, 26400 1100 (61%, 24400 12200 The system successfully implemented (39 examples) accomplish secondary several primary alcohols. Well-defined molecular Co(II) species are involved during catalysis, as inferred HRMS hot-filtration experiments. EPR studies magnetic moment measurements using Evans method demonstrate Co remains its +2 state an octahedral geometry throughout reaction. Pivotal evidence involvement β-hydride elimination leading acetophenone RDS catalyzed is obtained competitive deuterium labeling experiments, which indicative KIE 6.14. current report on base-metal catalysis high unprecedented turnovers (33200 16600 very short time (2 h) offers exciting atom-economical greener possibilities class synthetically valuable Guerbet-type reactions.

Язык: Английский

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Amine-functionalized bifunctional Co^III-NHC complexes: highly effective phosphine-free catalysts for the α-alkylation of nitriles

Chemical Communications, Год журнала: 2024, Номер 60(23), С. 3142 - 3145

Опубликована: Янв. 1, 2024

Newly developed amine functionalized NHC-supported Co

Язык: Английский

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Unravelling a bench-stable zinc-amide compound as highly active multitasking catalyst for radical-mediated selective alk(en)ylation of unactivated carbocycles under mild conditions

Chemical Science, Год журнала: 2024, Номер 15(14), С. 5238 - 5247

Опубликована: Янв. 1, 2024

The direct functionalization of unactivated organic moieties

Язык: Английский

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Direct Synthesis of Gem-β,β′-Bis(alkyl) Alcohols Using Nickel Catalysis via Sequential DCR Approach

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4018 - 4029

Опубликована: Фев. 28, 2024

Chemoselective synthesis of functionalized gem-β,β′-bis(alkyl)alcohols by coupling a β-alkylated secondary alcohol with primary is reported using nickel via sequential DCR (dehydrogenation–condensation–rehydrogenation) approach. Using our method, 1-arylethanol and benzyl alcohols undergo one-pot successive double alkylation reaction to form alcohols. Methanol, C2–C12 alcohols, citronellol, fatty acid-derived oleic are tolerated, including late-stage functionalization steroid hormones (cholesterol testosterone) 5-pregnen-3β-ol-20-one. The catalytic transformations enabled the donepezil drug (used for Alzheimer's disease), N-heteroarenes (quinoline acridine), chromane intermediate flavan derivatives. Hammett kinetic plot analysis differently p-substituted 1-phenyl propanol indicated that oxidation might be rate-determining step expected strong influence substitution on kinetics. A negative ρ value (−0.60) strongly signify formation positive charge alcohol. Preliminary mechanistic investigation revealed dehydrogenation aldehyde as it involves C–H/D bond breaking alcohol, PH/PD 6.0 was calculated. Reaction profile studies, EPR experiments, Hammett-plot cyclic voltammetry, UV–visible XPS analysis, structural electronic changes at Ni-center well behavior catalysts during progress reactions.

Язык: Английский

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Nickel-Catalyzed Cross-Electrophile Coupling of 1,2,3-Benzotriazin-4(3H)-ones with Aryl Bromides

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(24), С. 16567 - 16577

Опубликована: Дек. 1, 2022

The nickel-catalyzed cross-electrophile coupling of 1,2,3-benzotriazin-4(3H)-ones with aryl bromides to generate a diverse array ortho-arylated benzamide derivatives has been developed. reaction displayed good functional group tolerance Zn as the reductant. key this transformation is ring opening benzotriazinones, which undergo denitrogenative process obtain various (29 examples, 42-93% yield). scalability was demonstrated.

Язык: Английский

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