Mechanistic Diversity of Low-Valent Chromium Catalysis: Cross-Coupling and Hydrofunctionalization

Accounts of Chemical Research, Год журнала: 2021, Номер 54(8), С. 2014 - 2026

Опубликована: Апрель 8, 2021

ConspectusTransition-metal catalysis has traditionally been dominated by precious metals because of their high reactivity toward chemical transformations. As a cost-effective alternative, earth-abundant group 6 metal chromium is underdeveloped, and its remains largely unexplored, although the industrially important Phillips catalyst, which composed Cr as active metal, currently used to supply almost 40% total world demand for high-density polyethylene. served in organoreagents with high-valent states (≥2+), are typified reactions involving Nozaki–Hiyama–Kishi (NHK) Takai–Utimoto one-electron transfer processes. Given that low-valent usually facilitate process oxidative addition (OA), studying state provides opportunity develop new However, probably low stability reactive or lack catalytic activity structurally stable complexes, there limited success respect developing promoted Cr. In recent years, our probed adopting strategy forming situ. this Account, we detail efforts study behavior mechanism challenging transformations, such cleavage chemically inert bonds cross-coupling hydrofunctionalization arenes nitro motifs, strategies address prominent selectivity issues. We highlight finding Cr, being formed situ, possesses intriguing ability promote unactivated C–O, C–N, C–H achieve Kumada couplings even enable between two C(aryl)–O/C(aryl)–N bonds. During these processes, adopts high-spin interact chemicals, allowing insertion into σ-bonds. The OA model two-electron rarely considered allows breakage one cycle. This most transition suitable only bond catalysis. Mechanisms unusual, processes more often proposed, exemplified NHK reactions. These provide efficient functionalized benzaldehydes, amides, anilines, amines, levels selectivity. hope account will extend scope cognition

Язык: Английский

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Late-stage stitching enabled by manganese-catalyzed C─H activation: Peptide ligation and access to cyclopeptides

Science Advances, Год журнала: 2021, Номер 7(9)

Опубликована: Фев. 26, 2021

Earth-abundant manganese catalyst enabled the expedient synthesis of cyclic peptides via activation inert C─H bonds.

Язык: Английский

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Towards ligand simplification in manganese-catalyzed hydrogenation and hydrosilylation processes

Coordination Chemistry Reviews, Год журнала: 2022, Номер 458, С. 214421 - 214421

Опубликована: Янв. 31, 2022

Язык: Английский

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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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