N-Heterocyclic carbene-catalyzed desymmetrization of functionalized 1,4-dienes via Stetter Reaction

Lin, Qiqiao; Li, Yuanzhen; Das, Deb K.; Zhang, Guoxiang; Zhao, Zhigang; Yang, Shuang; Fang, Xinqiang

doi:10.1039/c6cc01011c

Cited by 36 publications

(15 citation statements)

References 46 publications

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“…61,63 These processes afforded, respectively, bicyclic (Scheme 30, a and b) 59,60 and tricyclic products (Scheme 30, c-e) [61][62][63] with two or more stereogenic centers, as well as cyclic ketone derivatives containing two contiguous tertiary/quaternary stereocenters (Scheme 30, f). 64 In each case, high yields and stereoselectivities were generally found. Interestingly, both the tricyclic and the cyclohexanone adducts could be used for useful synthetic transformations, including Pd-mediated cross-couplings 61 and -allylation reactions.…”

Section: Syn Thesismentioning

confidence: 92%

“…Intramolecular Stetter reactions mediated by chiral NHCs enable the asymmetric desymmetrization of cyclohexadienones [59][60][61][62][63] and 1,4-dienes 64…”

Section: Stetter Reactionsmentioning

confidence: 99%

“…Chiral aminoindanol triazolium salts were found to be optimal NHC precatalysts for desymmetrizing both cyclohexadienones and 1,4-dienes, 59,60,62,64 with cyclohexadiones also being effectively desymmetrized in the presence of a Dcamphor-derived NHC. 61,63 These processes afforded, respectively, bicyclic (Scheme 30, a and b) 59,60 and tricyclic products (Scheme 30, c-e) [61][62][63] with two or more stereogenic centers, as well as cyclic ketone derivatives containing two contiguous tertiary/quaternary stereocenters (Scheme 30, f).…”

Section: Syn Thesismentioning

confidence: 99%

“…Interestingly, both the tricyclic and the cyclohexanone adducts could be used for useful synthetic transformations, including Pd-mediated cross-couplings 61 and -allylation reactions. 64 When it comes to the desymmetrization of cyclohexadienones, detailed analyses have borne some remarkable achievements. Firstly, PKR was provided with cyclopentane-fused cyclohexadienones producing two structural isomers (1:1 ratio) with high enantioselectivity (Scheme 31).…”

Section: Syn Thesismentioning

confidence: 99%

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Kinetic Resolution, Dynamic Kinetic Resolution and Asymmetric Desymmetrization by N-Heterocyclic Carbene Catalysis

Risi¹,

Bortolini²,

Carmine³

et al. 2019

Synthesis

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N-Heterocyclic carbenes (NHCs) are now well-established organocatalysts for a large number of asymmetric and non-asymmetric transformations. In the last 15 years, there has been significant interest in using NHCs in kinetic resolution (KR), dynamic kinetic resolution (DKR) and asymmetric desymmetrization reactions for the stereoselective synthesis of enantioenriched compounds, with diverse substrates and activation modes being adopted to this end. This short review brings into focus the progress made on NHC-catalyzed KR, DKR, and asymmetric desymmetrization from 2004 until December 2018. The literature discussed in this article is classified on the basis of the type of reaction involving the NHC catalyst.1 Introduction2 Acylation Strategies2.1 O-Acylation2.2 N-Acylation2.3 C-Acylation3 Aldol-Acylation Processes4 Benzoin Reactions5 Stetter Reactions6 Miscellaneous Approaches7 Conclusion

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Section: Syn Thesismentioning

confidence: 92%

“…Intramolecular Stetter reactions mediated by chiral NHCs enable the asymmetric desymmetrization of cyclohexadienones [59][60][61][62][63] and 1,4-dienes 64…”

Section: Stetter Reactionsmentioning

confidence: 99%

Section: Syn Thesismentioning

confidence: 99%

Section: Syn Thesismentioning

confidence: 99%

See 2 more Smart Citations

Kinetic Resolution, Dynamic Kinetic Resolution and Asymmetric Desymmetrization by N-Heterocyclic Carbene Catalysis

Risi¹,

Bortolini²,

Carmine³

et al. 2019

Synthesis

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“…Electron‐deficient prochiral 1,4‐dienes were also able to be desymmetrized through NHC‐catalytic reactions. Fang, Yang, and co‐workers developed an enantioselective intramolecular Stetter reaction with NHC ent ‐ 88 used as the chiral catalyst to desymmetrize 1,4‐dienes 125 (Scheme ) . Various electron‐withdrawing groups could be installed on the alkene motifs with the desired annulation products 126 afforded in moderate to excellent yields and stereoselectivities.…”

Section: Desymmetrizations In Nhc Organocatalysismentioning

confidence: 99%

N‐Heterocyclic Carbene (NHC)‐Organocatalyzed Kinetic Resolutions, Dynamic Kinetic Resolutions, and Desymmetrizations

Wang

Pan

et al. 2018

Chemistry An Asian Journal

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The last couple of decades have witnessed tremendous development within N-heterocyclic carbene (NHC) organocatalysis. NHCs have been used as powerful organic catalysts in asymmetric synthesis. Although great achievements have been made in asymmetric NHC catalysis, their applications in kinetic resolution (KR), dynamic kinetic resolution (DKR), and desymmetrization processes have been relatively less developed. Moreover, limited activation modes have been involved in these processes. This review provides an overview of the NHC-organocatalyzed KR, DKR, and desymmetrization reactions in the preparation of chiral functional molecules. The aim is to highlight both the importance and elegance of these methods in the construction of challenging chiral compounds and to provide our own perspective on future development in this direction.

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The Catalytic Enantioselective Stetter Reaction

Flanigan¹,

Ozboya²,

Tanpure³

et al. 2021

Organic Reactions

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The catalytic enantioselective Stetter reaction is the coupling of an aldehyde with an electron‐deficient alkene via the conjugate addition of an acyl anion equivalent (Breslow intermediate) generated from the aldehyde and a chiral N ‐heterocyclic carbene (NHC) catalyst. The process affords 1,4‐dicarbonyl compounds and related systems, such as β‐nitroketones, in an efficient and atom‐economical fashion and with generally good‐to‐excellent enantioselectivities when fused polycyclic chiral triazolylidenes are employed as the NHC catalysts. The scope of the transformation is particularly broad for intramolecular reactions, but in the case of the intermolecular variant, only certain types of aldehyde donors and electrophilic alkenes can be successfully coupled together. This chapter describes theoretical and operational aspects of the catalytic enantioselective Stetter reaction such that the reader will be able to obtain optimal results in their own research. A detailed mechanistic overview is included to account for the factors that influence stereoselectivity and yield, and results from experimental and computational mechanistic studies are summarized. In addition, catalyst synthesis, reaction variants, applications in target‐directed synthesis, and comparison to other methods for generating 1,4‐dicarbonyl compounds are also presented. Tabular surveys are organized according to the modality of reactivity, either intra‐ or intermolecular, and the type of aldehyde donor. The literature is covered from the first disclosure of a catalytic enantioselective Stetter reaction in 1996 through to the end of 2019.

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N-Heterocyclic carbene-catalyzed desymmetrization of functionalized 1,4-dienes via Stetter Reaction

Cited by 36 publications

References 46 publications

Kinetic Resolution, Dynamic Kinetic Resolution and Asymmetric Desymmetrization by N-Heterocyclic Carbene Catalysis

Kinetic Resolution, Dynamic Kinetic Resolution and Asymmetric Desymmetrization by N-Heterocyclic Carbene Catalysis

N‐Heterocyclic Carbene (NHC)‐Organocatalyzed Kinetic Resolutions, Dynamic Kinetic Resolutions, and Desymmetrizations

The Catalytic Enantioselective Stetter Reaction

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