Chiral Primary–Secondary Diamines Catalyzed Michael–Aldol–Dehydration Reaction between Benzoylacetates and α,β‐Unsaturated Ketones: Highly Enantioselective Synthesis of Functionalized Chiral Cyclohexenones

Yang, Ying‐Quan; Chai, Zhuo; Wang, Haifeng; Chen, Xingkuan; Cui, Heng‐Lin; Zheng, Changwu; Xiao, Hua; Zhao, Gang

doi:10.1002/chem.200901541

Cited by 50 publications

(8 citation statements)

References 43 publications

(16 reference statements)

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“…Chiral primary-secondary diamines have also been found to catalyze Robinson annulations of activated b-ketoesters in the presence of an acidic additive (Scheme 54 a). [128,129] Further modification of the catalyst can even allow the formation of aq uaternary stereogenic center containing afluorine atom in 200 (Scheme 54 b). Under these conditions, aliphatic ketoesters generally give low yields,w hereas bketoamides can be good alternatives.…”

Section: Covalent Interaction:enamine/iminium Catalysismentioning

confidence: 99%

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

2017

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The Robinson annulation is a reaction that has been useful for numerous syntheses since its discovery in 1935, especially in the field of steroid synthesis. The products are usually obtained after three consecutive steps: the formation of an enolate (or derivative), a conjugate addition, and an aldol reaction. Over the years, several methodological improvements have been made for each individual step or alternative routes have been devised to access the Robinson annulation products. The first part of this Review outlines the most relevant developments towards the formation of monocarbonyl-derived Robinson annulation products (MRA products, MRAPs) and activated monocarbonyl-derived Robinson annulation products (AMRA products, AMRAPs). The following sections are then devoted to the diastereoselective and enantioselective synthesis of these products, while the last section describes the enantiomeric resolution of racemic mixtures.

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Section: Covalent Interaction:enamine/iminium Catalysismentioning

confidence: 99%

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

2017

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“…Further modification of the catalyst found that four-substituted-a,a-diaryl-prolinol 110 was most suitable for the epoxidation, offering high enantioselectivity for a wide range of enones [93]. An asymmetric organocatalytic tandem Micheal-aldol-dehydration reaction between benzolacetates and enones could be established by using chiral primarysecondary diamine 111 as a catalyst, giving rise to cyclohexenones in excellent ee values (Scheme 34) [94].…”

Section: Asymmetric Multicomponent and Domino Reactions Via Enamine Amentioning

confidence: 98%

Asymmetric Organocatalysis

Liu

Gong

2011

Asymmetric Catalysis From a Chinese Perspective

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Asymmetric organocatalysis has been receiving considerable attention in the last decade and thereby made tremendous advances. Chinese researchers have also intensified efforts to investigate asymmetric organocatalysis by using diverse types of disciplines, including enamine, iminium, Brønsted acid, carbene, and Lewis base catalysis. As a result, a large number of excellent catalysts and elegant protocols have come out from China. This article summarizes the most representative achievements in enantioselective organocatalysis from Chinese groups.

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“…Simple chiral primary-secondary diamine 74 was successfully employed by Zhao et al to induce the highly enantioselective domino Michael-aldol-dehydration reaction between benzoyl acetate and a,b-unsaturated ketones to furnish the corresponding functionalized chiral cyclohexenones 75a-e. [54] General enantioselectivities of at least 99% ee for both major and minor diastereomers were obtained combined with high yields and moderate to high diastereoselectivities (24-70% de), as shown in Scheme 19. The authors have explained the formation of 75a-e through a mechanism based on the iminium-enamine activation mode, which is depicted in Scheme 19.…”

Section: Domino Michael-aldol Reactionsmentioning

confidence: 97%

Recent Developments in Asymmetric Organocatalytic Domino Reactions

2012

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Since about the year 2000, the research area of asymmetric organocatalysis has grown rapidly to become one of the most fascinating and current fields in organic chemistry. In the last years, asymmetric domino reactions have widely benefited from this fast-growing field, as exemplified by the development of an explosive number of novel and powerful asymmetric organocatalytic domino processes, which allowed the easy construction of complex chiral molecular architectures from simple materials with high yields and very often remarkable enantioselectivities in a metal-free environment. Indeed, the possibility to join two or more organocatalytic reactions in one asymmetric domino process has become a challenging goal for chemists, due to several advantages from economical and environmental points of view, avoiding costly protecting groups and time-consuming purification procedures after each step, for example. This review aims to update the latest developments of this hot and fascinating field, covering the literature since the beginning of 2009.

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Chiral Primary–Secondary Diamines Catalyzed Michael–Aldol–Dehydration Reaction between Benzoylacetates and α,β‐Unsaturated Ketones: Highly Enantioselective Synthesis of Functionalized Chiral Cyclohexenones

Cited by 50 publications

References 43 publications

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

Asymmetric Organocatalysis

Recent Developments in Asymmetric Organocatalytic Domino Reactions

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