Transmetalation as Key Step in the Diastereo- and Enantioselective Synergistic Cu/Pd-Catalyzed Allylboration of Alkynes with Racemic Allylic Carbonates

Mateos, Jaime; Fuentes-Vara, Noelia; Fra, Laura; Rivera‐Chao, Eva; Vázquez‐Galiñanes, Nuria; Chaves-Pouso, Andrea; Fañanás‐Mastral, Martín

doi:10.1021/acs.organomet.0c00010

Cited by 18 publications

(15 citation statements)

References 60 publications

(32 reference statements)

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“…Notable contributions from Gong and Fu, as well as Fañanás-Mastral have illustrated methods utilizing alkynes as π-acceptors with allylic or propargylic alcohol derivatives (Scheme a), generating the boryl-functionalized skipped diene ( 114 ) or vinylallene ( 115 ) products. Fañanás-Mastral also examined the nature of the transmetalation by employing substrate 112c (Scheme b) . Complete inversion was observed indicating the organocopper had acted as a “hard” nucleophile via transmetalation and reductive elimination, instead of an outer-sphere process.…”

Section: Allylation/propargylationmentioning

confidence: 99%

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Copper-Catalyzed Borylative Difunctionalization of π-Systems

et al. 2020

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Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods to stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization of the π-system by the addition of an electrophile. This review covers known electrophiles to intercept catalytic intermediates in borylative difunctionalization strategies that have been reported up to the end of May 2020.

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Section: Allylation/propargylationmentioning

confidence: 99%

“…Fanãnaś-Mastral also examined the nature of the transmetalation by employing substrate 112c (Scheme 30b). 93 Complete inversion was observed indicating the organocopper had acted as a "hard" nucleophile via transmetalation and reductive elimination, instead of an outer-sphere process.…”

Section: Allylation/propargylationmentioning

confidence: 99%

Copper-Catalyzed Borylative Difunctionalization of π-Systems

et al. 2020

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“…Very recently, Fañanás-Mastral’s group has demonstrated that Cu-alkenylboranes, generated in situ from alkynes, can also be used as nonstabilized carbon nucleophiles in allylic substitutions with cyclic allylic carbonates, although the enantioselectivities were only moderate (up to 54% ee ). 432 …”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

“…Very recently, Fanãnaś-Mastral's group has demonstrated that Cu-alkenylboranes, generated in situ from alkynes, can also be used as nonstabilized carbon nucleophiles in allylic substitutions with cyclic allylic carbonates, although the enantioselectivities were only moderate (up to 54% ee). 432 Metalated 2-methyl-substituted 433 and related 2-substituted 434 pyridines were also successfully used as nucleophiles in this transformation by Trost and co-workers (Scheme 142). It was found that precomplexation of the pyridine unit to BF 3 • Et 2 O was necessary.…”

Section: Other C-nucleophilesmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

362

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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“…Recently, they have developed a diastereo-and enantioselective bimetallic Cu/Pd-catalyzed allylboration of terminal alkynes with racemic allyl carbonates and B 2 pin 2 (Scheme 23b). [140] The in situ generated β-borylalkenyl-copper species acts as a "hard" nucleophile and participate in the Pd-catalyzed allylation step with racemic allylic substrate to cause total inversion of configuration. Fu Group reported bimetallic Cu/Pd-catalyzed boryldifluoroallylation of alkynes to access gem-difluorodiene scaffolds under mild conditions with high regio-and stereoselectivity (Scheme 23c).…”

Section: Carboboration Of Alkynesmentioning

confidence: 99%

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

et al. 2021

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Organoboron compounds, especially alkenylboronates and arylboronates are highly useful reagents and versatile building blocks in the modern synthetic chemistry toolbox. This review focuses on copper-catalyzed routes to access alkenyl-and arylboronate esters. Various copper salts and ligands have been employed to access them in excellent regio-and stereoselectivity as well as high yields. Both addition and substitution reactions to alkenylboronates have been highlighted based on various methodologies including hydroboration, carboboration, borylative opening of propargyl three-and four-membered rings, dehalogenative borylation of alkenyl bromides and iodides, defluoroborylation of fluoroalkenes and direct C(sp 2 )À H bond activation of alkenes. Preparation of arylboronates involving borylation of aryl halides, C(sp 2 )À H borylation of arenes and cascade 1,3-halogen migration/borylation of 2halostyrenes have been reviewed. Mechanistic aspects of those borylation reactions are discussed briefly.

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Transmetalation as Key Step in the Diastereo- and Enantioselective Synergistic Cu/Pd-Catalyzed Allylboration of Alkynes with Racemic Allylic Carbonates

Cited by 18 publications

References 60 publications

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

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