Manganese-Catalyzed Direct Deoxygenation of Primary Alcohols

Bauer, Jonathan O.; Chakraborty, Subrata; Milstein, David

doi:10.1021/acscatal.7b01729

Cited by 91 publications

(53 citation statements)

References 69 publications

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“…In methanol solvent at 110 1C, the disclosed catalyst required a 2% mol loading for near quantitative conversions of starting amines with yields of 50-86% depending on the substrate. The same catalyst was found to be highly active in the ''dehydrogenative deoxygenation'' of alcohols 160 a combination of alcohol dehydrogenation to produce an aldehyde and subsequent Wolff-Kishner reduction of the aldehyde with hydrazine (Scheme 16). The same catalyst M-Mn-4 was shown to be superior to related A-Mn-2 and 3 in the latest report describing a-olefination of nitriles with primary alcohols as co-substrates.…”

Section: Dehydrogenation and Dehydrogenative Coupling Reactionsmentioning

confidence: 99%

Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

et al. 2018

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Catalytic hydrogenation and dehydrogenation reactions form the core of the modern chemical industry. This vast class of reactions is found in any part of chemical synthesis starting from the milligram-scale exploratory organic chemistry to the multi-ton base chemicals production. Noble metal catalysis has long been the key driving force in enabling these transformations with carbonyl substrates and their nitrogen-containing counterparts. This review is aimed at introducing the reader to the remarkable progress made in the last three years in the development of base metal catalysts for hydrogenations and dehydrogenative transformations.

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Section: Dehydrogenation and Dehydrogenative Coupling Reactionsmentioning

confidence: 99%

Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

et al. 2018

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“…In this process, the alcohol undertakes a concerted double proton transfer to yield the expected aldehyde in a single step. 17 Comparing the mechanisms, both are possible but the outer shell mechanism is favored. We also considered the transition from 3' to 1 but with a barrier of 44.3 kcal/mol above 3', this step is not competitive.…”

Section: Figurementioning

confidence: 99%

Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols

et al. 2019

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A recent study showed that a Mn-pincer could catalyze the acceptorless dehydrogenative coupling of nitriles and alcohols to yield acrylonitriles. The reaction mechanism proposed in that work contained some intermediates that, in most of the cases, were not characterized. Moreover, one of the intermediates involved a charged separation, which is unlikely in apolar solvents. To clarify the reaction mechanism of this critical reaction, we decided to perform a DFT study. Our results prove the existence of a cooperative effect of the metal and the ligand in several steps of the catalytic cycle. We also find the presence of several equilibria between isomeric intermediates where water, or the same alcohol reagent, take part in assisting the proton transfer. Furthermore, we have analyzed the charge separated structure proposed experimentally and have found a nearly pure covalent bond between the two expected charged moieties. Finally, the Knoevenagel condensation step that generates the acrylonitrile is found to be the rate-determining step.

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“…[8] Later on, Milsteinsg roup developed am ore sustainable version of the same transformation by using anon-noble-metal catalyst. [9] Despite significant advances such as those mentioned above,t he alcohol deoxygenation reaction is still limited to C À Oc leavage of one alcohol-containing molecule.D irect coupling of two alcohol molecules by ad ual-deoxygenation process could be an ideal approach for the production of highenergy-density hydrocarbons from oxygen-rich biomass feed-stocks.S uch transformations,w hich involve simultaneous cleavage of two inert CÀOb onds,a re very challenging, [10] although the corresponding mono-deoxygenation of alcohols with primary alcohols by ah ydrogen-borrowing strategy has been well developed. [11] To the best of our knowledge,o nly two examples of the full deoxygenative coupling of two alcohol-containing molecules have been reported.…”

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Manganese‐Catalyzed Dual‐Deoxygenative Coupling of Primary Alcohols with 2‐Arylethanols

et al. 2018

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Reported herein is ag eneral and efficient dualdeoxygenative coupling of primary alcohols with 2-arylethanols catalyzedb yawell-defined Mn/PNP pincer complex. This reaction is the first example of the catalytic dualdeoxygenation of alcohols using an on-noble-metal catalyst. Both deoxygenative homocoupling of 2-arylethanols (17 examples) and their deoxygenative cross-coupling with other primary alcohols (20 examples) proceeded smoothly to form the corresponding alkenes by ad ehydrogenation and deformylation reaction sequence. Scheme 1. Catalytic tandem dual-deoxygenative coupling of alcohols according to Obora et al. (2011) and Johnson et al. (2018).

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Manganese-Catalyzed Direct Deoxygenation of Primary Alcohols

Cited by 91 publications

References 69 publications

Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols

Manganese‐Catalyzed Dual‐Deoxygenative Coupling of Primary Alcohols with 2‐Arylethanols

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