Chiral Brønsted Acid-Catalyzed Enantioselective Three-Component Povarov Reaction

Liu, Hua; Dagousset, Guillaume; Masson, Géraldine; Retailleau, Pascal; Zhu, Jieping

doi:10.1021/ja900806q

Cited by 386 publications

(151 citation statements)

References 39 publications

(15 reference statements)

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“…However, whether the reaction benefits from large proximal sterics or small depends on the sterics of the nucleophile. For smaller displaced nucleophiles, large proximal sterics are advantageous, disfavouring Type I E pathways 29, 33, 35, 36, 37, 38, 72, 73, 74, 75, 76, 77, 78. However, if the nucleophile is large, small proximal sterics are essential 32, 34, 39, 79, 80.…”

Section: Resultsmentioning

confidence: 99%

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Selecting Chiral BINOL‐Derived Phosphoric Acid Catalysts: General Model To Identify Steric Features Essential for Enantioselectivity

Reid

Goodman

2017

Chemistry A European J

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Choosing the optimal catalyst for a new transformation is challenging because the ideal molecular requirements of the catalyst for one reaction do not always simply translate to another. Large groups at the 3,3′ positions of the binaphthol rings are important for efficient stereoinduction but if they are too large this can lead to unusual or poor results. By applying a quantitative steric assessment of the substituents at the 3,3′ positions of the binaphthol ring, we have systematically studied the effect of modulating this group on enantioselectivity for a wide range of reactions involving imines, and verified this analysis using ONIOM calculations. We have shown that in most reactions, the stereochemical outcome depends on both proximal and remote sterics. Summarising detailed calculations into a simple qualitative model identifies and explains the steric features required for high selectivity. This model is consistent with seventy seven papers reporting reactions (over 1000 transformations in total), and provides a straightforward decision tree for selecting the best catalyst.

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Section: Resultsmentioning

confidence: 99%

“…The reactants and the phosphoric acid moiety of the catalyst were included in the high‐layer, and the remaining regions of the catalyst were treated as the low‐layer. This method has previously been shown to give excellent results when used to describe reactions catalyzed by chiral phosphoric acids 4, 16, 18, 34, 35, 36, 37…”

Section: Methodsmentioning

confidence: 99%

Selecting Chiral BINOL‐Derived Phosphoric Acid Catalysts: General Model To Identify Steric Features Essential for Enantioselectivity

Reid

Goodman

2017

Chemistry A European J

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“…The first highly enantioselective example of this type of reaction was developed by . [180] Indeed, the reaction of a wide variety of aromatic and aliphatic aldehydes as well as anilines with benzyl N-vinylcarbamate 389 in the presence of BINOL-derived phosphoric acid 390 afforded the corresponding chiral (2,4-cis)-4-amino-2-arylA C H T U N G T R E N N U N G (alkyl)-tetrahydroquinolines 391a-j in good to high yields (64-90%) and remarkable enantioselectivities (92 to > 99% ee), as shown in Scheme 102.…”

Section: Miscellaneous Multicomponent Reactionsmentioning

confidence: 99%

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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“…Proof of this substantial progress is the employment of such privileged class of Brønsted acids in the total syntheses of significant compounds as, for instance: ()-arboricine A [66], (S)-anabasine [67], monastrol [68], ()-zampanolide [69], (+)-galipinine [70,71], (+)-cuspareine [70], ()-angusturine [70,72], and torcetrapib [73] (Fig XII.6). More recently, a Brønsted acid organocatalyzed nucleophilic substitution reaction of 3-hydroxindoles 8 with ene-carbamates 9 was successfully developed by Gong's group for its application in the first catalytic enantioselective synthesis of (+)-folicanthine [75], member of the large cyclotryptamine alkaloid family which exhibit fascinating biological and pharmaceutical activities [76].…”

Section: Xii31 Phosphoric Acidsmentioning

confidence: 99%