Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect

Coordination Chemistry Reviews, Год журнала: 2021, Номер 451, С. 214257 - 214257

Опубликована: Окт. 28, 2021

Язык: Английский

---

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

Organic Letters, Год журнала: 2021, Номер 23(3), С. 869 - 875

Опубликована: Янв. 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.

Язык: Английский

---

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

---

Enable biomass-derived alcohols mediated alkylation and transfer hydrogenation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 15, 2024

A single-atom catalyst with generally regarded inert Zn–N4 motifs derived from ZIF-8 is unexpectedly efficient for the activation of alcohols, enabling alcohol-mediated alkylation and transfer hydrogenation. C-alkylation nitriles, ketones, N-heterocycles, amides, keto acids, esters, N-alkylation amines amides all go smoothly developed method. Taking α-alkylation nitriles alcohols as an example, starts (1) nitrogen-doped carbon support catalyzed dehydrogenation into aldehydes, which further condensed to give vinyl followed by (2) hydrogenation C=C bonds in on sites. The experimental results DFT calculations reveal that Lewis acidic Zn-N4 sites promote step activating alcohols. This first example highly catalysts various organic transformations biomass-derived alkylating reagents hydrogen donors. Using carbonyl compounds or synthesis α-alkylated appealing a sustainability perspective. Here, acting acid effectively activates thus promoting reactions using both

Язык: Английский

---

Iron-Catalyzed α-Methylation of Ketones Using Methanol as the C1 Source under Photoirradiation

Organic Letters, Год журнала: 2022, Номер 24(33), С. 6219 - 6223

Опубликована: Авг. 12, 2022

A mild, environmentally benign approach for α-methylation of ketones utilizing methanol as the C1 source under visible light has been developed. The reaction conditions were favorable a wide range with both aromatic and aliphatic backbones, allowing good-to-excellent yields respective products. tentative mechanism is postulated after preliminary mechanistic kinetic experiments.

Язык: Английский

---

Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Язык: Английский

---

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

ChemCatChem, Год журнала: 2020, Номер 13(3), С. 934 - 939

Опубликована: Ноя. 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.

Язык: Английский

---

Nickel‐Catalyzed Selective Synthesis of α‐Alkylated Ketones via Dehydrogenative Cross‐Coupling of Primary and Secondary Alcohols

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 364(1), С. 47 - 52

Опубликована: Окт. 11, 2021

Abstract Herein, we describe an isolable, air‐stable, homogeneous, nickel catalyst that performs dehydrogenative cross‐coupling reaction between secondary and primary alcohols to result α‐alkylated ketone products selectively. The sequence of steps involve in this one‐pot is dehydrogenation both alcohols, condensation the aldehyde, hydrogenation situ‐generated α,β‐unsaturated ketone. Preliminary mechanistic investigation hints a radical mechanism following borrowing hydrogen reaction. magnified image

Язык: Английский

---

Cobalt-Catalyzed Alkylation of Nitriles with Alcohols

Organometallics, Год журнала: 2022, Номер 41(22), С. 3145 - 3151

Опубликована: Фев. 17, 2022

Herein, we report an operationally convenient, cobalt-catalyzed alkylation of aryl nitriles employing primary and secondary alcohols (>30 examples, up to 86% yield). The use readily available cobalt precursors the widely employed BIAN (BIAN = bis(arylimino)acenaphthene) ligand affords efficient catalytic reaction that is environmentally benign, leading formation water as only byproduct.

Язык: Английский

---

Recent advances in C/N-alkylation with alcohols through hydride transfer strategies

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(39), С. 7713 - 7745

Опубликована: Янв. 1, 2022

Recent advances in C/N alkylation using alcohols as alkylating reagents via hydrogen-shuttle methodologies: Borrowing Hydrogen, Acceptorless Dehydrogenative Coupling, and Base-mediated Hydride Transfer.

Язык: Английский

---