Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism

Gao, Yang; Hill, David E.; Wei, Hao; McNicholas, Brendon J.; Vantourout, Julien C.; Hadt, Ryan G.; Reisman, Sarah E.; Blackmond, Donna G.; Baran, Phil S.

doi:10.1021/jacs.1c03007

Cited by 92 publications

(61 citation statements)

References 92 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, Reisman, Blackmond, and Baran developed electrochemical, catalytic NHTK-type reactions using alkenyl halides and NHPI esters, 25 achieving wide substrate scope with a simple setup (Scheme 5). 30 The catalytic NHTK protocol using a chemical reducing reagent (Zn, Mn, Mg powder) was not applicable to NHPI esters. They supposed that rapid and selective cathodic reduction of chromium(III) is key to the efficient reaction progress.…”

Section: Short Review Synthesismentioning

confidence: 99%

Recent Progress in Chromium-Mediated Carbonyl Addition Reactions

Katayama¹,

Mitsunuma²,

Kanai³

2021

Synthesis

View full text Add to dashboard Cite

Organochromium(III) species are versatile nucleophiles in complex molecule synthesis due to their high functional group tolerance and chemoselectivity for aldehydes. Traditionally, carbonyl addition reactions of organochromium(III) species were performed through reduction of organohalides either using stoichiometric chromium(II) salts or catalytic chromium salts in the presence of stoichiometric reductants (such as manganese(0)). Recently, alternative methods emerged involving organoradical formation from readily available starting materials (e.g. N-hydroxyphthalimide esters, alkenes, and alkanes), followed by trapping the radical with stoichiometric or catalytic chromium(II) salts. Such methods, especially using catalytic chromium(II) salts, will lead to the development of sustainable chemical processes minimizing salt wastes and number of synthetic steps. In this review, we describe methods for generation of organochromium(III) species for addition reactions to carbonyl compounds, classified by nucleophiles.

show abstract

Section: Short Review Synthesismentioning

confidence: 99%

Recent Progress in Chromium-Mediated Carbonyl Addition Reactions

Katayama¹,

Mitsunuma²,

Kanai³

2021

Synthesis

View full text Add to dashboard Cite

show abstract

“…The resultant organochromium species serves as the reactive nucleophile. While substantial efforts have been made to generalize the NHK reaction and render chromium catalytic, most practical applications use a substantial excess . Organometallic nucleophiles are still broadly used in carbonyl addition, , though progress toward the development of catalytic carbonyl reductive couplings by using nonmetallic reductants (H 2 , 2-PrOH) and related hydrogen autotransfer reactions has been made …”

Section: Introductionmentioning

confidence: 99%

Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5-Diaza-3,7-diphosphacyclooctane Ligand

et al. 2021

View full text Add to dashboard Cite

We report a catalytic method to access secondary alcohols by the coupling of aryl iodides. Either aldehydes or alcohols can be used as reaction partners, making the transformation reductive or redox-neutral, respectively. The reaction is mediated by a Ni catalyst and a 1,5-diaza-3,7-diphosphacyclooctane. This P2N2 ligand, which has previously been unrecognized in cross-coupling and related reactions, was found to avoid deleterious aryl halide reduction pathways that dominate with more traditional phosphines and NHCs. An interrupted carbonyl-Heck type mechanism is proposed to be operative, with a key 1,2-insertion step forging the new C–C bond and forming a nickel alkoxide that may be turned over by an alcohol reductant. The same catalyst was also found to enable synthesis of ketone products from either aldehydes or alcohols, demonstrating control over the oxidation state of both the starting materials and products.

show abstract

“…The field of C–C cross-coupling reactions, in which organometallic catalysts are integral, can also benefit from the mild conditions used in electrocatalysis that foster selectivity and group tolerance. While the electrocatalytic versions of many reductive cross-couplings have been known for a long time (see section III.A.2 ), 38 the approach can extend to C–C forging from advanced synthons, as for instance between aldehydes and vinyl bromides (Nozaki–Hiyama–Kishi coupling) 131 or ketones and olefins. 132 Following this track while integrating some reminiscence of the EHC described above could for instance enable a molecularly electrocatalyzed coupling of ketones with vinyl halides or alkynes into tertiary vinyl alcohols ( Figure 15 b).…”

Section: Future Directionsmentioning

confidence: 99%

Electrocatalysis with Molecular Transition-Metal Complexes for Reductive Organic Synthesis

Kaeffer

Leitner

2022

JACS Au

View full text Add to dashboard Cite

Electrocatalysis enables the formation or cleavage of chemical bonds by a genuine use of electrons or holes from an electrical energy input. As such, electrocatalysis offers resource-economical alternative pathways that bypass sacrificial, waste-generating reagents often required in classical thermal redox reactions. In this Perspective, we showcase the exploitation of molecular electrocatalysts for electrosynthesis, in particular for reductive conversion of organic substrates. Selected case studies illustrate that efficient molecular electrocatalysts not only are appropriate redox shuttles but also embrace the features of organometallic catalysis to facilitate and control chemical steps. From these examples, guidelines are proposed for the design of molecular electrocatalysts suited to the reduction of organic substrates. We finally expose opportunities brought by catalyzed electrosynthesis to functionalize organic backbones, namely using sustainable building blocks.

show abstract

Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism

Cited by 92 publications

References 92 publications

Recent Progress in Chromium-Mediated Carbonyl Addition Reactions

Recent Progress in Chromium-Mediated Carbonyl Addition Reactions

Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5-Diaza-3,7-diphosphacyclooctane Ligand

Electrocatalysis with Molecular Transition-Metal Complexes for Reductive Organic Synthesis

Contact Info

Product

Resources

About