Palladium‐Catalyzed Asymmetric Intramolecular Reductive Heck Desymmetrization of Cyclopentenes: Access to Chiral Bicyclo[3.2.1]octanes

Yuan, Zhenbo; Feng, Ziwen; Zeng, Yuye; Zhao, Xiaobin; Lin, Aijun; Yao, Hequan

doi:10.1002/ange.201900059

Cited by 13 publications

(3 citation statements)

References 49 publications

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“…Importantly, the resultant bicyclic[3.3.1]nonanones formed by this method are prevalent in natural products (Scheme 1c). 13,14 In this article, we describe the development of an intramolecular desymmetric α-arylation and α-alkenylation of cyclohexanones using benzylamine and a chiral palladium phosphinooxazoline complex 15 as dual catalysts. 16 We demonstrate that aryl/alkenyl bromides and their triflate surrogates can be employed as substrates to provide the corresponding quaternary carbon products in excellent yields with high enantioselectivities.…”

Section: ■ Introductionmentioning

confidence: 99%

Enantioselective Access to γ-All-Carbon Quaternary Center-Containing Cyclohexanones by Palladium-Catalyzed Desymmetrization

Wei

Cai

et al. 2019

ACS Catal.

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An efficient desymmetrization of γ-quaternary carbon-containing cyclohexanones using readily available Pd/ (S)-t BuPhox and benzylamine as dual catalysts is reported. We describe herein the development of the reaction, exploration of the substrate scope, and studies on the reaction mechanism. The intramolecular coupling reaction leads to the formation of bicyclo[3.3.1]nonanones with a quaternary carbon bridgehead in synthetically useful yields (up to 98%) with high enantioselectivities (up to 98:2 er) and good functional group tolerance (>30 examples). Significantly, aryl and alkenyl bromides as well as less reactive triflates are all compatible substrates for this process. The synthetic versatility of this strategy is demonstrated by scale-up synthesis and diverse transformations of the products into valuable building blocks, including quaternary center-containing dihydronaphthalenes, ring-fused indoles and lactones, tetralones, and 6,6,5-tricycles. Mechanistic studies by computational calculations provide insights into the role of benzylamine in accelerating the reaction rate and enhancing the enantioselectivities.

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Section: ■ Introductionmentioning

confidence: 99%

Enantioselective Access to γ-All-Carbon Quaternary Center-Containing Cyclohexanones by Palladium-Catalyzed Desymmetrization

Wei

Cai

et al. 2019

ACS Catal.

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“…12 In 2018, Hayashi's group reported a Rh-catalyzed desymmetrization hydroarylation of divinylphosphine oxides to synthesize P-chiral phosphine oxides (Scheme 1c). 13 However, methods that can take advantage of asymmetric desymmetrization for the simultaneous synthesis of chiral phosphorus and quaternary carbon stereocenters remain underdeveloped.…”

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confidence: 99%

Palladium-Catalyzed Asymmetric Desymmetrization for the Simultaneous Construction of Chiral Phosphorus and Quaternary Carbon Stereocenters

Zhou,

Xue,

Zhou

et al. 2024

Org. Lett.

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“…However, the synthesis of chiral quaternary carbon centers is a challenging task, especially those that are not formed at the direct reaction site [31][32][33][34][35][36][37][38][39][40][41] . Asymmetric desymmetrization of prochiral compounds or meso-compounds offers a commendable synthetic tool for achieving this objective [42][43][44][45][46][47][48][49][50][51][52][53][54] .…”

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confidence: 99%

Rhodium-catalyzed intermolecular enantioselective Alder–ene type reaction of cyclopentenes with silylacetylenes

Zhang

et al. 2021

Nat Commun

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The Alder–ene type reaction between alkenes and alkynes provides an efficient and atom-economic method for the construction of C-C bond, which has been widely employed in the synthesis of natural products and other functional molecules. The intramolecular enantioselective Alder-ene cycloisomerization reactions of 1,n-enynes have been extensively investigated. However, the intermolecular asymmetric version has not been reported, and remains a challenging task. Herein, we describe a rhodium-catalyzed intermolecular enantioselective Alder-ene type reaction of cyclopentenes with silylacetylenes. A variety of chiral (E)-vinylsilane tethered cyclopentenes bearing one quaternary carbon and one tertiary carbon stereocenters are achieved in high yields and enantioselectivities. The reaction undergoes carbonyl-directed migratory insertion, β-H elimination and desymmetrization of prochiral cyclopentenes processes.

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Palladium‐Catalyzed Asymmetric Intramolecular Reductive Heck Desymmetrization of Cyclopentenes: Access to Chiral Bicyclo[3.2.1]octanes

Cited by 13 publications

References 49 publications

Enantioselective Access to γ-All-Carbon Quaternary Center-Containing Cyclohexanones by Palladium-Catalyzed Desymmetrization

Enantioselective Access to γ-All-Carbon Quaternary Center-Containing Cyclohexanones by Palladium-Catalyzed Desymmetrization

Palladium-Catalyzed Asymmetric Desymmetrization for the Simultaneous Construction of Chiral Phosphorus and Quaternary Carbon Stereocenters

Rhodium-catalyzed intermolecular enantioselective Alder–ene type reaction of cyclopentenes with silylacetylenes

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