Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

Guo, Yafei; Kootstra, Johanan; Harutyunyan, Syuzanna R.

doi:10.1002/ange.201808392

Cited by 6 publications

(3 citation statements)

References 44 publications

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“…[5,6] This widely accepted reaction model has been demonstrated by a series of elegant studies, and enantioselective pathways have also been realized via diverse catalytic systems, including transition metals and organocatalysts (Scheme 1a). [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] This 100 % atom-economic process can be used to construct enantioenriched stereogenic centers remote from versatile electron-deficient functional groups and thus represents a highly valuable route to build intriguing chiral skeletons. However, overturning the aforementioned classical viewpoint, that is, the introduction of a nucleophile to the electronically mismatched C5position via umpolung 1,5-addition, is very challenging, and a related general protocol remains absent.…”

Section: Introductionmentioning

confidence: 99%

“…Nucleophilic 1,6‐conjugate addition is a well‐known transformation, and generally involves sequential electronically matched nucleophilic addition and protonation [5, 6] . This widely accepted reaction model has been demonstrated by a series of elegant studies, and enantioselective pathways have also been realized via diverse catalytic systems, including transition metals and organocatalysts (Scheme 1a) [7–21] . This 100 % atom‐economic process can be used to construct enantioenriched stereogenic centers remote from versatile electron‐deficient functional groups and thus represents a highly valuable route to build intriguing chiral skeletons.…”

Section: Introductionmentioning

confidence: 99%

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Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

et al. 2022

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Electronically matched nucleophilic 1,6-conjugate addition has been well studied and widely applied in synthetic areas. In contrast, nucleophilic 1,5-conjugate addition represents an electronically forbidden process and is considered unfeasible. Here, we describe modular protocols for 1,5-conjugate addition reactions via palladium hydride catalysis. Both palladium and synergistic Pd/organocatalyst systems are developed to catalyze 1,5conjugate reaction, followed by inter-or intramolecular [3+2] cyclization. A migratory 1,5-addition protocol is established to corroborate the feasibility of this umpolung concept. The 1,5-addition products are conveniently transformed into a series of privileged enantioenriched motifs, including polysubstituted tetrahydrofuran, dihydrofuran, cyclopropane, cyclobutane, azetidine, oxetane, thietane, spirocycle and bridged rings. Preliminary mechanistic studies corroborate the involvement of palladium hydride catalysis.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

et al. 2022

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“…In view of the above achievements, we are interested in developing a catalytic asymmetric conjugate 1,6allylation with more general substrate structure and broader substrate scope. Copper(I)-catalyzed asymmetric 1,6-addition with alkyl metal reagents (such as organozinc reagent and Grignard reagent) has been reported as a powerful tool to regioselectively construct carbon-carbon bonds [34][35][36][37][38][39][40][41][42][43][44][45][46] . Herein, we disclose an asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-one with a copper(I)-NHC catalyst (Fig.…”

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confidence: 99%

Copper(I)-catalyzed asymmetric 1,6-conjugate allylation

et al. 2020

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Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones. The phenolic hydroxyl group in NHC ligands is found to be pivotal to obtain the desired products. Both aryl group and alkyl group at δ-position are well tolerated with the corresponding products generated in moderate to high yields and high enantioselectivity. Moreover, both 2-substituted and 3-substituted allylboronates serve as acceptable allylation reagents. At last, the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups.

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Enantioselective Hydrocarbamoylation of Alkenes

2022

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The asymmetric hydroaminocarbonylation of olefins represents a straightforward approach for the synthesis of enantioenriched amides, but is hampered by the necessity to employ CO gas, often at elevated pressures. We herein describe, as an alternative, an enantioselective hydrocarbamoylation of alkenes leveraging dual copper hydride and palladium catalysis to enable the use of readily available carbamoyl chlorides as a practical carbamoylating reagent. The protocol is applicable to various types of olefins, including alkenyl arenes, terminal alkenes, and 1,1-disubstituted alkenes. Substrates containing a diverse range of functional groups as well as heterocyclic substructures undergo functionalization to provide α-and β-chiral amides in good yields and with excellent enantioselectivities.

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Catalytic Regio‐ and Enantioselective Alkylation of Conjugated Dienyl Amides

Cited by 6 publications

References 44 publications

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

Umpolung Asymmetric 1,5‐Conjugate Addition via Palladium Hydride Catalysis

Copper(I)-catalyzed asymmetric 1,6-conjugate allylation

Enantioselective Hydrocarbamoylation of Alkenes

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