Regioselectivity Umpolung in Asymmetric Diels–Alder Reaction of <i>ortho</i>-Formyl-Substituted Cinnamates and Dienals via Double Aminocatalysis

Lu, Jian-Bin; Shi, Chong-Hui; Hu, Di; Gao, Xin-Yue; Chen, Zhichao; Du, Wei; Chen, Ying‐Chun

doi:10.1021/acs.orglett.0c03862

Cited by 9 publications

(6 citation statements)

References 52 publications

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“…Recently, Chen group has applied the trienanmine catalyzed [4+2] cycloaddition of dienals 20 on the ortho‐ formyl cinnamates 21 by differentiating double amino catalysis (Scheme 4). [11] …”

Section: Amino‐organo Synergistic Catalysismentioning

confidence: 99%

Synergistic Strategies in Aminocatalysis

Vecchio

Sinibaldi

Nori

et al. 2022

Chemistry A European J

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Synergistic catalysis offers the unique possibility of simultaneous activation of both the nucleophile and the electrophile in a reaction. A requirement for this strategy is the stability of the active species towards the reaction conditions and the two concerted catalytic cycles. Since the beginning of the century, aminocatalysis has been established as a platform for the stereoselective activation of carbonyl compounds through HOMO-raising or LUMO-lowering. The burgeoning era of aminocatalysis has been driven by a deep understanding of these activation and stereoinduction modes, thanks to the introduction of versatile and privileged chiral amines. The aim of this review is to cover recent developments in synergistic strategies involving aminocatalysis in combination with organo-, metal-, photo-, and electrocatalysis, focusing on the evolution of privileged aminocatalysts architectures.

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Section: Amino‐organo Synergistic Catalysismentioning

confidence: 99%

Synergistic Strategies in Aminocatalysis

Vecchio

Sinibaldi

Nori

et al. 2022

Chemistry A European J

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“…In terms of selectivity, DA cycloaddition is a well‐known phenomenon that contributes to the expansion of a wide range of compounds with intricate capabilities and controlled stereochemistry [37–39] . Numerous synthetic accomplishments have been established so far with exceptional efficacy based on various selectivity characteristics in order to create top‐notch organic frameworks [40–45] . This review aims to compile the work based on selectivity in cycloaddition protocols to generate a systematic, synthetically valuable composition in organic synthesis, inspired by the distinct results accumulated by the DA reaction.…”

Section: Selectivity In Diels‐alder Cycloaddition Pathwaymentioning

confidence: 99%

Regioselectivity Switch Towards the Development of Innovative Diels‐Alder Cycloaddition and Productive Applications in Organic Synthesis

2022

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The Diels‐Alder (DA) reaction is one of the fascinating synthetic strategies known for its pericyclic action and concerted mechanism that leads to various targets. Numerous synthetic pursuits have been rewarded with conceptually distinct and efficient ways. To date, extensive and spectacular accomplishments have been made in the field of Diels‐Alder chemistry to overcome the complexities of organic synthesis that inspired organic chemists to focus on expanding and establishing the postulates. In principle, DA reactions are governed by their straightforward reactivity pattern with a high degree of certainty, primarily attributed to the HOMO‐LUMO separation of reacting partners. Furthermore, general forecasts rely on account of background studies, conveniently hypothesizing the stereochemical outcomes and reaction dynamic pathways. DA has recently emerged as a technique for establishing a variety of products from the same reacting species under varying reaction conditions rather than a general reactivity profile. Such exceptional results are of significant interest in organic synthesis to pursue the challenges of unanticipated product establishment. Herein, we summarize the impressive finding of the remarkable switch in the regioselectivity and diastereoselectivity of DA reactions under a diverse set of reaction protocols in light of Diels‐Alder's unending importance in chemical science. This review aims to establish a beneficial account of Diels‐Alder towards the astonishing switches extended to study varying synthetic versions in organic synthesis protocols attributed to natural and biologically active scaffolds. This review also provides insight into distinct reaction dynamics in DA reactions that are subjected to access molecular frameworks ranging from simple to complicated ones to foster high levels of innovation in chemical sciences.

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“… 3 On the contrary, the pathway relying on the activation of both substrates by two molecules of the same catalyst is much less explored. 4 In this type of approach, electronic properties of substrates are enhanced and at the same time differentiated via the formation of both LUMO-lowered and HOMO-raised reactive intermediates. Therefore, such catalytic activation can be referred to as differentiating catalysis.…”

mentioning

confidence: 99%

“…The main tool used for this type of asymmetric synthesis is synergistic catalysis where two different catalysts independently activate two substrates, thus providing chiral intermediates capable of participating in a given transformation . On the contrary, the pathway relying on the activation of both substrates by two molecules of the same catalyst is much less explored . In this type of approach, electronic properties of substrates are enhanced and at the same time differentiated via the formation of both LUMO-lowered and HOMO-raised reactive intermediates.…”

mentioning

confidence: 99%

Differentiating Catalysis in the Dearomative [4 + 2]-Cycloaddition Involving Enals and Heteroaromatic Aldehydes

2022

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In this paper, the application of differentiating catalysis in the [4 + 2]-cycloaddition between 2-alkyl-3-formylheteroarenes and α,β-unsaturated aldehydes is described. Within the developed approach, the same aminocatalyst is employed for the independent activation of both starting materials, differentiating their properties via LUMO-lowering and HOMO-rising principles. By the combination of dearomative dienamine activation with iminium ion chemistry high enantio- and diastereoselectivity of the doubly asymmetric process was accomplished. Selected transformations of products were also demonstrated.

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Regioselectivity Umpolung in Asymmetric Diels–Alder Reaction of ortho-Formyl-Substituted Cinnamates and Dienals via Double Aminocatalysis

Cited by 9 publications

References 52 publications

Synergistic Strategies in Aminocatalysis

Synergistic Strategies in Aminocatalysis

Regioselectivity Switch Towards the Development of Innovative Diels‐Alder Cycloaddition and Productive Applications in Organic Synthesis

Differentiating Catalysis in the Dearomative [4 + 2]-Cycloaddition Involving Enals and Heteroaromatic Aldehydes

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