Oxidation–reductive coupling of alcohols catalyzed by oxo-vanadium complexes

Steffensmeier, Eric; Nicholas, Kenneth M.

doi:10.1039/c7cc08387d

Cited by 26 publications

(28 citation statements)

References 60 publications

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“…This is confirmed by the 1 H NMR spectrum after the reaction ( Figure S4), in which a singlet is observed at 4.68 ppm and a doublet is observed at 7.71 ppm; these signals are diagnostic for the methine H atoms of 1,1,2,2-tetraphenylethane and the o-H atoms of benzophenone, respectively. 21 Observation of the ketone byproduct suggests that the reaction proceeds through the previously reported mechanism in which the alcohol acts as a reductant. This reaction can be successfully extended to other benzyl alcohol derivatives ( Table 1, entries 2 and 3, and Figures S5 and S6), an attractive class of substrates that can be derived from lignin biomass.…”

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confidence: 80%

“…Reaction conditions similar to those employed by Nicholas and co-workers were used. 21 Gratifyingly, heating a C 6 D 6 solution of benzhydrol with 5 mol % of dimer 1 provides full conversion to the desired product with concomitant formation of benzophenone ( Table 1, entry 1). This is confirmed by the 1 H NMR spectrum after the reaction ( Figure S4), in which a singlet is observed at 4.68 ppm and a doublet is observed at 7.71 ppm; these signals are diagnostic for the methine H atoms of 1,1,2,2-tetraphenylethane and the o-H atoms of benzophenone, respectively.…”

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confidence: 99%

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Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Griffin

Schafer

2020

Inorg. Chem.

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The reductive coupling of alcohols using vanadium pyridonate catalysts is reported. This attractive approach for C(sp 3 )−C(sp 3 ) bond formation uses an oxophilic, earth-abundant metal for a catalytic deoxygenation reaction. Several pyridonate complexes of vanadium were synthesized, giving insight into the coordination chemistry of this understudied class of compounds. Isolated intermediates provide experimental mechanistic evidence that complements reported computational mechanistic proposals for the reductive coupling of alcohols. In contrast to previous mononuclear vanadium(V)/vanadium(III)/vanadium(IV) cycles, this pyridonate catalyst system is proposed to proceed by a vanadium(III)/vanadium(IV) cycle involving bimetallic intermediates.

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confidence: 80%

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confidence: 99%

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Griffin

Schafer

2020

Inorg. Chem.

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“…Metal-catalyzed CÀOb ond homolysis is also promising for alcohol deoxygenation. [7] However,t he substrate scope is restricted to benzylic and allylic alcohols.Recently,Liand coworkers reported amore efficient deoxygenation of alcohols by at andem reaction that involves dehydrogenation and Wolff-Kishner reduction, catalyzed by either aR uo rI r catalyst. [8] Later on, Milsteinsg roup developed am ore sustainable version of the same transformation by using anon-noble-metal catalyst.…”

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confidence: 99%

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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“…Seeking more economical catalysts for oxo-metal promoted reductive coupling of alcohols, a set of Z + [LV v O 2 ]complexes (L = N,O-bi-, tri-dentate ligands) was tested for the coupling of benzhydrol by PPh 3 at 150 °C (Scheme 19). 30 The unexpected non-consumption of PPh 3 and equimolar formation of benzophenone, in contrast to the Re-catalyzed reductive couplings, 27 indicates that the alcohol substrate serves as the reductant. Several benzylic and allylic alcohols were similarly converted into the corresponding dimers in moderate to high yields (32-100%).…”

Section: Scheme 18 Molybdate-catalyzed Hydrogenolysis and Dimerizationmentioning

confidence: 99%

Deoxygenative Transition-Metal-Promoted Reductive Coupling and Cross-Coupling of Alcohols and Epoxides

Bandari¹,

Nicholas²

2020

Synthesis

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The prospective utilization of abundant, CO2-neutral, renewable feedstocks is driving the discovery and development of new reactions that refunctionalize oxygen-rich substrates such as alcohols and polyols through C–O bond activation. In this review, we highlight the development of transition-metal-promoted reactions of renewable alcohols and epoxides that result in carbon–carbon bond-formation. These include reductive self-coupling reactions and cross-coupling reactions of alcohols with alkenes and arene derivatives. Early approaches to reductive couplings employed stoichiometric amounts of low-valent transition-metal reagents to form the corresponding hydrocarbon dimers. More recently, the use of redox-active transition-metal catalysts together with a reductant has enhanced the practical applications and scope of the reductive coupling of alcohols. Inclusion of other reaction partners with alcohols such as unsaturated hydrocarbons and main-group organometallics has further expanded the diversity of carbon skeletons accessible and the potential for applications in chemical synthesis. Catalytic reductive coupling and cross-coupling reactions of epoxides are also highlighted. Mechanistic insights into the means of C–O activation and C–C bond formation, where available, are also highlighted.1 Introduction2 Stoichiometric Reductive Coupling of Alcohols3 Catalytic Reductive Coupling of Alcohols3.1 Heterogeneous Catalysis3.2 Homogeneous Catalysis4 Reductive Cross-Coupling of Alcohols4.1 Reductive Alkylation4.2 Reductive Addition to Olefins5 Epoxide Reductive Coupling Reactions6 Conclusions and Future Directions

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Oxidation–reductive coupling of alcohols catalyzed by oxo-vanadium complexes

Cited by 26 publications

References 60 publications

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

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

Deoxygenative Transition-Metal-Promoted Reductive Coupling and Cross-Coupling of Alcohols and Epoxides

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