Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis

Crabtree, Robert H.

doi:10.1021/acs.chemrev.6b00556

Cited by 505 publications

(235 citation statements)

References 162 publications

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“…[5] Following the concept of HA, pyrroles can be synthetized from unsaturated 1,4-diols and primary amines. [5] Following the concept of HA, pyrroles can be synthetized from unsaturated 1,4-diols and primary amines.…”

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confidence: 99%

Manganese‐Catalyzed Multicomponent Synthesis of Pyrroles through Acceptorless Dehydrogenation Hydrogen Autotransfer Catalysis: Experiment and Computation

et al. 2019

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An ew base metal catalyzed sustainable multicomponent synthesis of pyrroles from readily available substrates is reported. The developed protocolu tilizes an air-and moisture-stable catalyst system and enablest he replacement of themutagenic ahaloketones with readily abundant 1,2-diols. Moreover,the presented method is catalytic in base and the sole byproducts of this transformation are water and hydrogen gas. Experimental and computationalm echanistic studies indicatet hat the reactiont akes place through ac ombineda cceptorless dehydrogenation hydrogenautotransfermethodology.Multicomponent reactions are valuable sustainable processes for the construction of complex molecules in one pot from three or more substrates. This strategy merges severale lementary reaction steps, which leads to minimization of the amount of waste, and simplifies the workup and purifications teps. [1] Pyrroles represent prominent and important chemicalm otifs in medicinal, agro, and advanced materials chemistry.C lassical synthetic routes suffer from drawbacks mainly resultingf rom the generation of substantial amounts of waste produced during the multi-stepp re-functionalization of substrates or byproduct formation. [2] Accordingly,t here is ac ontinuous need to develop new catalytic systems that allow the direct and atom-economic conversion of renewable and readily available substrates to pyrroles.Alcohols can be obtained from renewable biomass resources and presentp romising sustainable feedstock chemicals. The utilization of alcohols as substrates in the synthesis of fine chemicals will hence contributen ot only to the reduction of toxic chemical waste but also to decrease CO 2 emissions by avoidingthe use of carbon fossil sources. [3] One of the key concepts for alcoholf unctionalization is hydrogen autotransfer (HA), which has become ap owerful tool for utilizing abundant alcohols as building blocks for environmentally benign CÀC and CÀNb ondf ormations, releasing water as the only byproduct (Scheme 1A). [4] Ar elatedc oncept is acceptorless dehydrogenation(AD), which permits the conversion of alcohols to car-Scheme1.Acceptorless dehydrogenation and hydrogen autotransfer catalysis.

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confidence: 99%

Manganese‐Catalyzed Multicomponent Synthesis of Pyrroles through Acceptorless Dehydrogenation Hydrogen Autotransfer Catalysis: Experiment and Computation

et al. 2019

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“…[12] Over the last few decades,t hese reactions have been advanced by using precious and toxic noble-metal-based catalysts. [12] Over the last few decades,t hese reactions have been advanced by using precious and toxic noble-metal-based catalysts.…”

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confidence: 99%

Manganese‐Catalyzed Direct Olefination of Methyl‐Substituted Heteroarenes with Primary Alcohols

2018

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Herein, we present the first catalytic direct olefination of methyl-substituted heteroarenes with primary alcohols through an acceptorless dehydrogenative coupling. The reaction is catalyzed by a complex of the earth-abundant transition metal manganese that is stabilized by a bench-stable NNN pincer ligand derived from 2-hydrazinylpyridine. The reaction is environmentally benign, producing only hydrogen and water as byproducts. A large number of E-disubstituted olefins were selectively obtained with high efficiency.

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“…The activated intermediate could couple with other molecules to form more complex molecules, the unsaturated bonds of which could then be reduced to furnish a hydrogen‐borrowing/‐autotransfer process . Alternatively, the metal hydride could be protonated to release hydrogen gas or accepted by an oxidant to accomplish a dehydrogenative coupling process (Scheme , middle) –,. The selectivity between these two processes has rarely been addressed but appears to be determined by the nature of catalyst used, and different catalysts are required to achieve either hydrogen‐borrowing or dehydrogenative coupling.…”

Section: Methodsmentioning

confidence: 99%

Atmosphere‐Controlled Chemoselectivity: Rhodium‐Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols

Liu

Tang

et al. 2017

Chemistry A European J

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The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen‐borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.

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Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis

Cited by 505 publications

References 162 publications

Manganese‐Catalyzed Multicomponent Synthesis of Pyrroles through Acceptorless Dehydrogenation Hydrogen Autotransfer Catalysis: Experiment and Computation

Manganese‐Catalyzed Multicomponent Synthesis of Pyrroles through Acceptorless Dehydrogenation Hydrogen Autotransfer Catalysis: Experiment and Computation

Manganese‐Catalyzed Direct Olefination of Methyl‐Substituted Heteroarenes with Primary Alcohols

Atmosphere‐Controlled Chemoselectivity: Rhodium‐Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols

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