Copper-Catalyzed Asymmetric Borylallylation of Vinyl Arenes

Kim, Namhyeon; Han, Jung Tae; Ryu, Do Hyun; Yun, Jaesook

doi:10.1021/acs.orglett.7b03022

Cited by 54 publications

(18 citation statements)

References 43 publications

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“…improved this reaction and extended the alkene substrate to styrenes. High ee values and yields were usually obtained under these reaction conditions . Very recently, Hoveyda et al.…”

Section: Copper Catalysismentioning

confidence: 87%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

244

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Three-component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition-metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom- and step-economic efficiency. This Focus Review highlights recent advances in this field.

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“…improved this reaction and extended the alkene substrate to styrenes. High ee values and yields were usually obtained under these reaction conditions . Very recently, Hoveyda et al.…”

Section: Copper Catalysismentioning

confidence: 87%

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Zhang

Liu

Chen

et al. 2018

Chemistry An Asian Journal

244

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“…1). [13] Although only three examples of alkene benzylboration were disclosed with styrene, a vinyl boronate, and a vinyl silane, this work nevertheless demonstrated the viability of a fully intermolecular 1,2-carboboration, setting the stage for further development to unlock the full potential of this transformation in organic synthesis.…”

Section: Three-component Alkene Carboboration Reactionsmentioning

confidence: 89%

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Liu

Gao

Zeng

et al. 2019

Israel Journal of Chemistry

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During the past decade, many research groups have described catalytic methods for 1,2-carboboration, allowing access to structurally complex organoboronates from alkenes. Various transition metals, especially copper, palladium, and nickel, have been widely used in these reactions. This review summarizes advances in this field, with a special focus on the catalytic cycles involved in different metal-catalyzed carboboration reactions, as well as the regio-and stereochemical consequences of the underlying mechanisms. 1,2-Carboboration of other unsaturated systems, such as alkynes and allenes, is outside of the scope of this review. Scheme 1. General depiction of catalyst-controlled 1,2-carboboration. In this scheme and throughout the manuscript, nucleophilic reaction partners are drawn in blue, and electrophilic reaction partners are drawn in red. Scheme 4. Cu(I)-catalyzed borylative radical cyclization. Scheme 5. Cu(I)-catalyzed intramolecular carboboration involving an aldol cyclization. Scheme 6. Cu(I)-catalyzed intramolecular acylboration.Review Isr. J. Chem. 2020, 60, 219 -229 Scheme 7. Cu(I)-catalyzed divergent alkylboration of alkenes. Scheme 8. Cu(I)-catalyzed alkene carboboration with aldehydes as the electrophile. Scheme 9. Cu(I)-catalyzed three-component acylboration. Scheme 10. Cu(I)-catalyzed heteroarylboration of 1,3-dienes.

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“…From our earlier report on the borylative coupling of vinyl arenes with primary allylic electrophiles, we found that the use of allyl phosphates and N , N ‐dimethylacetylamide (DMA) solvent were crucial for good yield of product in the presence of a catalytic amount of CuCl and a chiral bisphosphine ligand. However, application of the previous reaction conditions to secondary allylic phosphate ( rac ‐ 2 a ) resulted in moderate yield and enantioselectivity despite promising E / Z selectivity.…”

Section: Methodsmentioning

confidence: 99%

“…[8,9] In particular,f ew examples of allylic substitutions of chiral alkylcopper speciesw ere reported with simple allyl electrophiles in respective reports by other groups [10] and our group (Scheme1a). [11] Although these methods were highly efficient, the reactions accommodated only simple allyl electrophiles, and the reaction with ar acemic secondary allylic electrophile resulted in am ixture of E/Z stereoisomers. [11a] Controlling E/Z selectivity in the copper-catalyzed allylic substitutionh as been an important issue as it creates an additional stereocomponenta nd, thus, stereochemically well-defined prochiral allylic electrophileso rc yclic electrophiles had to be used for high stereocontrol.…”

mentioning

confidence: 99%

Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates

Han

Kim

Baik

et al. 2020

Chemistry A European J

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Copper‐catalyzed stereoconvergent allylation of chiral sp3‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing (E)‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3)‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)‐olefin formation from racemic allylic phosphates.

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Copper-Catalyzed Asymmetric Borylallylation of Vinyl Arenes

Cited by 54 publications

References 43 publications

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Transition‐Metal‐Catalyzed 1,2‐Carboboration of Alkenes: Strategies, Mechanisms, and Stereocontrol

Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates

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