Chiral Brønsted Acid-Catalyzed Enantioselective Multicomponent Mannich Reaction: Synthesis of <i>anti</i>-1,3-Diamines Using Enecarbamates as Nucleophiles

Dagousset, Guillaume; Drouet, Fleur; Masson, Géraldine; Zhu, Jieping

doi:10.1021/ol9023985

Cited by 117 publications

(48 citation statements)

References 80 publications

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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%

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%

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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“…[94] d) Organocatalytic asymmetric Mannich 3CR using chiral phosphoric acid 120. [95] Newly formed bonds are indicated in red. Cbz = benzyloxycarbonyl, Ts = 4toluenesulfonate.…”

Section: Discussionmentioning

confidence: 99%

“…[89] For example, acid-catalyzed classical MCRs such as the Hantzsch, [62] Biginelli, [15] Povarov, [90] and Mannich [91] reactions have greatly benefited from the recent rise of chiral Brønsted acid catalysis (Scheme 14). [92][93][94][95] Other recent developments in organocatalysis have led to the development of a number of very elegant asymmetric cascade processes. [96] Several classical MCRs have also benefitted from other developments in asymmetric organocatalysis.…”

Section: Towards Stereoselective Mcrsmentioning

confidence: 99%

Multicomponent Reaction Design in the Quest for Molecular Complexity and Diversity

2011

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Multicomponent reactions have become increasingly popular as tools for the rapid generation of small-molecule libraries. However, to ensure sufficient molecular diversity and complexity, there is a continuous need for novel reactions. Although serendipity has always played an important role in the discovery of novel (multicomponent) reactions, rational design strategies have become much more important over the past decade. In this Review, we present an overview of general strategies that allow the design of novel multicomponent reactions. The challenges and opportunities for the future will be discussed.

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“…The reaction provides direct access to β‐amino carbonyl compounds which are found as the key substructure of many natural products , possess a wide array of biological activities , and are key versatile intermediates in synthetic organic chemistry . Many one‐pot procedures are offered in recent years to widen the synthetic scope of the Mannich reaction by using asymmetric catalysis , aqueous conditioned reactions , high pressure induced by water‐freezing , rare earth metal containing catalysts , Lewis acids , and silyl enol ethers .…”

Section: Introductionmentioning

confidence: 99%

Antiselective Three‐Component Mannich Reactions in Thiopyran‐4‐one System

Abaee

Mojtahedi

Akbari

et al. 2012

Journal of Heterocyclic Chem

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The one‐pot, three‐component Mannich reactions of thiopyran‐4‐one 1 with different aromatic aldehydes and aniline derivatives in the presence of catalytic quantities of ZrOCl2.8H2O (15 mol %) led to rapid and high yield formation of various 3‐methylamino substituted derivatives of 1 at room temperature. Spectroscopic and X‐ray analyses of the products suggested the formation of the anti stereoisomers as the major product of the reactions.

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Chiral Brønsted Acid-Catalyzed Enantioselective Multicomponent Mannich Reaction: Synthesis of anti-1,3-Diamines Using Enecarbamates as Nucleophiles

Cited by 117 publications

References 80 publications

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

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

Multicomponent Reaction Design in the Quest for Molecular Complexity and Diversity

Antiselective Three‐Component Mannich Reactions in Thiopyran‐4‐one System

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