A revisit to proline-catalyzed amination under basic conditions: Insight into the key intermediates and stereocontrolling transition state models for the reversal of enantioselectivity

Fu, Aiping; Tian, Changke; Li, Hongliang; Li, Ping; Chu, Tianshu; Wang, Zonghua; Liu, Jingquan

doi:10.1016/j.chemphys.2015.04.013

Cited by 5 publications

(1 citation statement)

References 37 publications

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“…In the absence of DBU, DEAD attacks the syn -face of the s-trans -enamine with a concomitant hydrogen-bonding stabilization. In the presence of DBU anti -addition to the electrophile of the s-trans -enamine carboxylate or the ion pair generates the ( S )-product. , …”

Section: Stereodivergence In Acyclic Systemsmentioning

confidence: 98%

Stereodivergent Catalysis

2018

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This review covers diastereo- and enantiodivergent catalyzed reactions in acyclic and cyclic systems using metal complexes or organocatalysts. Among them, nucleophilic addition to carbon-carbon and carbon-nitrogen double bonds, α-functionalization of carbonyl compounds, allylic substitutions, and ring opening of oxiranes and aziridines are considered. The diastereodivergent synthesis of alkenes from alkynes is also included. Finally, stereodivergent intramolecular and intermolecular cycloadditions and other cyclizations are also reported.

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Section: Stereodivergence In Acyclic Systemsmentioning

confidence: 98%

Stereodivergent Catalysis

2018

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Reactions of Aldehydes and Ketones and Their Derivatives

Murray¹

2019

Organic Reaction Mechanisms Series

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Mechanistic Study on the Asymmetric Synthesis of the Wieland‐Miescher Ketone and Analogs

et al. 2019

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The organocatalyzed synthesis of the Wieland‐Miescher ketone (WMK) via N‐sulfonyl‐binamprolinamide catalysis was investigated using experimental and computational tools. A mechanistic proposal is presented describing the origin of the high enantioselectivity, which rivals that of aldolases. The computational study reveals that the role of the prolinamide catalyst is to lower the reaction barrier and determine the stereoselectivity of the product achieved, while the role of the carboxylic acid is to facilitate proton transfer steps. The effect of the acid co‐catalyst was confirmed by experiments. The role of the structure of the BINAM backbone and the effect of the sulfonamide group are uncovered experimentally and computationally. Calculations show that a rigid highly defined catalytic pocket due to covalent and steric interactions induces conformational changes in the triketone substrate to maximize interactions.

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A revisit to proline-catalyzed amination under basic conditions: Insight into the key intermediates and stereocontrolling transition state models for the reversal of enantioselectivity

Cited by 5 publications

References 37 publications

Stereodivergent Catalysis

Stereodivergent Catalysis

Reactions of Aldehydes and Ketones and Their Derivatives

Mechanistic Study on the Asymmetric Synthesis of the Wieland‐Miescher Ketone and Analogs

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