Highly Enantioselective Cu‐Catalyzed Conjugate Additions of Dialkylzinc Reagents to Unsaturated Furanones and Pyranones: Preparation of Air‐Stable and Catalytically Active Cu–Peptide Complexes

Brown, M. Kevin; Degrado, Sylvia J.; Hoveyda, Amir H.

doi:10.1002/ange.200501251

Cited by 30 publications

(12 citation statements)

References 45 publications

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“…In our quest for the design of readily available and efficient chiral ligands for asymmetric organometallic catalysis, we have recently developed "one-step and quantitatively available" ligands-the diphenylphosphinoazomethinylate salts (DiPPAM). [11] The DiPPAM L2 (Figure 1), which is structurally related to "small peptide ligands", [12] has already proved its efficiency for copper-catalyzed 1,6-ACA of di alkylzinc reagents to cyclic dienones. [5c, e] These results encouraged us to investigate the more challenging Cu-catalyzed 1,6-ACA of dialkylzinc reagents to linear dienones, using some chiral ligands including our DiPPAM ligand.…”

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confidence: 99%

Enantioselective 1,6‐Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu‐DiPPAM Complex—Extension to Asymmetric Sequential 1,6/1,4‐Conjugate Addition

Magrez-Chiquet

Morin

Wencel‐Delord

et al. 2013

Chemistry A European J

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confidence: 99%

Enantioselective 1,6‐Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu‐DiPPAM Complex—Extension to Asymmetric Sequential 1,6/1,4‐Conjugate Addition

Magrez-Chiquet

Morin

Wencel‐Delord

et al. 2013

Chemistry A European J

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“…Due to their favorable biological activities, various catalytic synthetic strategies have been devised for their efficient asymmetric synthesis. Hoveyda and co‐workers described an enantioselective synthesis of chromanones via a Cu‐catalyzed addition of dialkylzinc to enones 2. In their recent study, Scheidt et al.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Synthesis of Chromanones via a Tryptophan‐ Derived Bifunctional Thiourea‐Catalyzed Oxa‐Michael–Michael Cascade Reaction

et al. 2011

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Tryptophan-derived tertiary amine-thiourea catalysts were shown to promote a cascade oxaMichael-Michael reaction between ethylene b-keto esters and nitroolefins, resulting in the formation of 3,3-disubstituted 4-chromanones bearing a quaternary center in high diastereoselectivity and enantioselectivity. The chromanone products can be readily converted to biologically important fused and spiro tricyclic chromans.Keywords: bifunctional catalysts; cascade reactions; chromanones; chromans; tryptophan Chiral chromans and chromanones are important structural motifs that are abundant in natural products and a wide range of biologically significant molecules.[1] Due to their favorable biological activities, various catalytic synthetic strategies have been devised for their efficient asymmetric synthesis. Hoveyda and co-workers described an enantioselective synthesis of chromanones via a Cu-catalyzed addition of dialkylzinc to enones.[2] In their recent study, Scheidt et al. utilized an intramolecular conjugate addition strategy for the enantioselective synthesis of flavanones and chromanones.[3] Subsequently, Feng and coworkers reported an enantioselective synthetic strategy, based on chiral N,N'-dioxide Ni(II)-catalyzed intramolecular oxa-Michael addition to a,b-unsaturated ketones.[4] Organocatalytic cascade reactions [5] have also been employed for the construction of chromans and chromanones. Wang and co-workers developed a cascade oxa-Michael-Michael for the facile construction of chiral chromans via an aminal intermeidate. [6] A cascade Michael-aldol sequence has been employed by Hong and Córdova for the asymmetric construction of chromans and chromenes, respectively. [7] Despite the aforementioned elegant synthetic strategies, to the best of our knowledge, an organocatalytic cascade reaction leading to chiral chromanones bearing a quaternary stereogenic center has yet to be reported. [8] It is thus desirable to devise an efficient synthetic strategy to access this type of novel structural motifs.The creation of quaternary stereogenic centers is a challenging task in organic synthesis.[9] As part of our continuing efforts towards the enantioselective generation of quaternary stereocenters, [10] we became interested in the synthesis of chiral chromanones containing an all-carbon quaternary center. We envisioned that an intramolecular oxa-Michael addition of phenol to an activated alkene, followed by a subsequent intermolecular Michael addition to an nitroolefin might provide a facile one-pot synthesis of highly functionalized 3,3-disubstituted 4-chromanones bearing a quaternary stereogenic center (Scheme 1). A bifunctional tertiary amine-thiourea catalyst [11] appears Scheme 1. Synthesis of chromanones and tricyclic chromans via an oxa-Michael-Michael cascade reaction.

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“… 193 Hoveyda and co-workers disclosed that the amino acid based phosphine L34 could be employed to promote the catalytic ACA of dialkylzinc reagents to 2(5 H )-furanone ( Scheme 75 ). 194 The reaction was carried out in the presence of an aldehyde to trap the enolate intermediate, thus preventing adventitious ketene formation or intermolecular Michael addition. The resulting aldol products could be further oxidized to afford the corresponding diketones 163 in high yields and up to 97% ee.…”

Section: Furanone Derivatives As Electrophilesmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones

2017

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γ-Butenolides, γ-butyrolactones, and derivatives, especially in enantiomerically pure form, constitute the structural core of numerous natural products which display an impressive range of biological activities which are important for the development of novel physiological and therapeutic agents. Furthermore, optically active γ-butenolides and γ-butyrolactones serve also as a prominent class of chiral building blocks for the synthesis of diverse biological active compounds and complex molecules. Taking into account the varying biological activity profiles and wide-ranging structural diversity of the optically active γ-butenolide or γ-butyrolactone structure, the development of asymmetric synthetic strategies for assembling such challenging scaffolds has attracted major attention from synthetic chemists in the past decade. This review offers an overview of the different enantioselective synthesis of γ-butenolides and γ-butyrolactones which employ catalytic amounts of metal complexes or organocatalysts, with emphasis focused on the mechanistic issues that account for the observed stereocontrol of the representative reactions, as well as practical applications and synthetic potentials.

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Highly Enantioselective Cu‐Catalyzed Conjugate Additions of Dialkylzinc Reagents to Unsaturated Furanones and Pyranones: Preparation of Air‐Stable and Catalytically Active Cu–Peptide Complexes

Cited by 30 publications

References 45 publications

Enantioselective 1,6‐Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu‐DiPPAM Complex—Extension to Asymmetric Sequential 1,6/1,4‐Conjugate Addition

Enantioselective 1,6‐Conjugate Addition of Dialkylzinc Reagents to Acyclic Dienones Catalyzed by Cu‐DiPPAM Complex—Extension to Asymmetric Sequential 1,6/1,4‐Conjugate Addition

Enantioselective Synthesis of Chromanones via a Tryptophan‐ Derived Bifunctional Thiourea‐Catalyzed Oxa‐Michael–Michael Cascade Reaction

Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones

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