Electrochemical asymmetric epoxidation of olefins by using an optically active Mn-salen complex

Tanaka, Hideo; Kuroboshi, Manabu; Takeda, H.; Kanda, Hisaaki; Torii, S.

doi:10.1016/s0022-0728(01)00387-4

Cited by 65 publications

(50 citation statements)

References 47 publications

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“…To date, electrochemically driven hydrofunctionalization of alkenes is unknown, and electrosynthetic methods that enable asymmetric alkene functionalization remain elusive. [23][24][25] Against this backdrop, we describe an electrochemical approach for the enantioselective hydrocyanation of conjugated alkenes powered by a Co/Cu dual electrocatalytic process.…”

Section: Introductionmentioning

confidence: 99%

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

et al. 2020

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Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, we address this long-standing synthetic problem using an electrocatalytic strategy. Electrochemistry allows for the seamless combination of two classic radical reactions-cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation-to accomplish highly enantioselective hydrocyanation without the need for stoichiometric oxidant. We harness electrochemistry's unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis sheds light on the origin of enantioinduction, for which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions that direct the enantio-determining C-CN bond formation. This discovery demonstrates the power of electrochemistry in accessing new chemical space and providing solutions to pertinent challenges in synthetic chemistry. File list (2) download file view on ChemRxiv 01_Lin_MS.pdf (1.70 MiB) download file view on ChemRxiv 00_Lin_TOC.png (333.52 KiB)

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Section: Introductionmentioning

confidence: 99%

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

et al. 2020

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“…Although this intermediate was competent in oxidizing styrene derivatives to their epoxides, the selectivity and efficiency were much lower than those of desired model compound I (which is isoelectronic to oxoiron(V)). Collman and coworkers 50 and Tanaka and coworkers 51 reported electrochemical epoxidation using Mn complexes (porphyrins and salen), but the mechanism involved the electrochemical generation of the chemical oxidant (H 2 O 2 and OCl À ), which would subsequently activate the metal complex in a process similar to chemical oxidation. Murray and coworkers 52 and recently Dey and coworkers 35 showed electrochemical reductive activation of O 2 bound to metal porphyrin complexes, which would subsequently form high-valent oxometal intermediates to catalyze oxidation reactions.…”

Section: Resultsmentioning

confidence: 99%

Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and CC bonds using water as the oxygen source

et al. 2020

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“…In 2001, Tanaka et al. reported an asymmetric electrochemical epoxidation reaction mediated by a chiral Mn complex 17 a (Scheme ) . The electrochemical process was conducted in two phases.…”

Section: Chiral Catalystmentioning

confidence: 99%

“…In 2001, Tanaka et al reported an asymmetrice lectrochemical epoxidation reactionm ediated by ac hiralM nc omplex 17 a (Scheme 17). [39] The electrochemical process was conducted in two phases.H ypochlorite, generated in situ from anodico xidation of chloride in the aqueous phase, oxidized Mn-complex 17 a to its active metal oxide form 17 b in the organic phase. The metal oxide then delivered its oxygen to the alkenes,p roducing the desired epoxides with moderate to good enantioselectivity.…”

Section: Metal Catalysismentioning

confidence: 99%

Asymmetric Electrochemical Catalysis

Lin

Luo

2019

Chemistry A European J

140

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Asymmetric electrochemical catalysis, an emerging frontline in asymmetric catalysis and electro‐organic synthesis, is summarized. Representative works are classified, with respect to the external chiral resources, including chiral media, chiral mediator, chiral catalyst, and chiral electrode. This concept article is expected to provide readers with the general concepts and perspectives of each chiral electrochemical catalysis mode, and to indicate the potential and future development of asymmetric electrochemical catalysis.

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Electrochemical asymmetric epoxidation of olefins by using an optically active Mn-salen complex

Cited by 65 publications

References 47 publications

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and CC bonds using water as the oxygen source

Asymmetric Electrochemical Catalysis

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