Design and Synthesis of Tunable Chiral 2,2′‐Bipyridine Ligands: Application to the Enantioselective Nickel‐Catalyzed Reductive Arylation of Aldehydes

Zhang, Shuai; Perveen, Saima; Ouyang, Yizhao; Xu, Liang; Yu, Tao; Zhao, Min; Wang, Linghua; Song, Peidong; Li, Pengfei

doi:10.1002/anie.202117843

Cited by 56 publications

(31 citation statements)

References 85 publications

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“…To embark on the investigation, 2‐chloro‐3,4‐dimethoxybenzaldehyde ( 1 ) was chosen as the model substrate (Table 1). The SBpy‐type chiral ligands L1 ‐ L4 were prepared based on our previous synthetic route [18a–c] . After extensive experimentation, a set of “standard conditions” was established in which the desired reductive coupling product 2 could be produced in 92 % yield and 95 : 5 er.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

et al. 2022

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The first nickel‐catalyzed highly enantioselective reductive Ullmann coupling of ortho‐chlorinated aryl aldehyde was achieved under mild reaction conditions with a chiral 2,2′‐bipyridine ligand (+)‐DTB‐SBpy, thus providing axially chiral biphenyl or binaphthyl dials with up to 99 % yield and 99.5:0.5 er. The versatility of the products as common synthetic intermediates for diverse axially chiral ligands, catalysts, and functional molecules was demonstrated by short‐step transformations. This protocol also allowed the concise and highly enantioselective formal total synthesis of biologically active natural products (+)‐kotanin, (−)‐isoschizandrin and (+)‐gossypol.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

et al. 2022

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“…Further mechanistic investigation revealed that the migratory insertion of the aldehyde into an aryl cobalt species was the rate-determining step of the reductive addition reaction. We believe this work represents a new and sustainable avenue for the rapid construction of highly significant chiral benzyl alcohols …”

Section: Discussionmentioning

confidence: 97%

Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides

Jiang

Yang

et al. 2022

J. Am. Chem. Soc.

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Grignard addition is one of the most important methods used for syntheses of alcohol compounds and has been known for over a hundred years. However, research on asymmetric catalysis relies on the use of organometallic nucleophiles. Here, we report the first visible-light-induced cobalt-catalyzed asymmetric reductive Grignard-type addition for synthesizing chiral benzyl alcohols (>50 examples, up to 99% yield, and 99% ee). This methodology has the advantages of mild reaction conditions, good functionality tolerance, excellent enantiocontrol, the avoidance of mass metal wastes, and the use of precious metal catalysts. Kinetic realization studies suggested that migratory insertion of an aryl cobalt species into the aldehyde was the rate-determining step of the reductive addition reaction.

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“…Chemie medium gave slightly lower er value in comparison with the ternary system and for the latter two solvents, the yield was also significantly lower (entries [14][15][16].…”

Section: Methodsmentioning

confidence: 99%

Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

et al. 2022

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In contrast to previous approaches to chiral α‐aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel‐catalyzed general, efficient and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions using atmospheric CO2 has been developed. A unique chiral 2,2′‐bipyridine ligand named Me‐SBpy featuring compact polycyclic skeleton enabled both high reactivity and stereoselectivity. The utility of this method has been demonstrated by synthesis of various chiral α‐aryl carboxylic acids (30 examples, up to 95 % yield and 99 : 1 er), including profen family anti‐inflammatory drugs and transformations using the acids as key intermediates. Based on mechanistic experimental results, a plausible catalytic cycle involving Ni‐complex/radical equilibrium and Lewis acid‐assisted CO2 activation has been proposed.

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Design and Synthesis of Tunable Chiral 2,2′‐Bipyridine Ligands: Application to the Enantioselective Nickel‐Catalyzed Reductive Arylation of Aldehydes

Cited by 56 publications

References 85 publications

Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides

Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

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