Starke und sterisch begrenzte Säuren kontrollieren fünf stereogene Zentren in der katalytischen asymmetrischen Diels‐Alder‐Reaktion von Cyclohexadienonen mit Cyclopentadien

Ghosh, Santanu; Das, Sayantani; De, Chandra Kanta; Yepes, Diana; Neese, Frank; Bistoni, Giovanni; Leutzsch, Markus; List, Benjamin

doi:10.1002/ange.202000307

Angewandte Chemie

2020

DOI: 10.1002/ange.202000307

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Starke und sterisch begrenzte Säuren kontrollieren fünf stereogene Zentren in der katalytischen asymmetrischen Diels‐Alder‐Reaktion von Cyclohexadienonen mit Cyclopentadien

Santanu Ghosh

Sayantani Das

Chandra Kanta De

et al.

Abstract: Wir stellen eine hochenantioselektiven Diels‐Alder‐Reaktion zwischen kreuzkonjugierten Cyclohexadienonen und Cyclopentadien vor, in der fünf Stereozentren durch den stark sauren und sterisch eingeschränkten Imidodiphosphorimidat‐Katalysator kontrolliert werden. Darüber hinaus zeigen wir Methoden auf, die damit gewonnenen Produkte in weithin nutzbare Intermediate umzuwandeln, sowie eine quantenchemische Studie, die es uns ermöglichte, einen tieferen Einblick in den Reaktionsmechanismus zu gewinnen und die stere… Show more

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Cited by 7 publications

References 52 publications

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Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

Zhao

Zhang

et al. 2021

Angewandte Chemie

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The enantioselective aza‐Diels–Alder reaction is efficient for constructing chiral tetrahydropyridines, but the catalytic asymmetric aza‐Diels–Alder reaction of ketimines with unactivated dienes is still a challenging topic. Herein, guided by computational screening, a highly enantioselective aza‐Diels–Alder reaction of 2‐aryl‐3H‐indol‐3‐ones with unactivated dienes was realized by using a B(C6F5)3/chiral phosphoric acid catalyst system under mild conditions. The reaction has a broad scope with respect to both aza‐Diels–Alder reaction partners and hence offers rapid access to an array of tetrahydropyridine derivatives with pretty outcomes (up to 99 % yield, >20:1 dr and 98:2 er). The reaction is very efficient: lowering catalyst loadings for the model reaction to 0.1 mol %, enantioselectivity is still maintained. The synthetic utility was confirmed by transformations of the products. DFT calculations provide convincing evidence for the interpretation of stereoselection.

show abstract

Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

Zhao

Zhang

et al. 2021

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Predicting Highly Enantioselective Catalysts Using Tunable Fragment Descriptors**

et al. 2023

Self Cite

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Catalyst optimization processes typically rely on inductive and qualitative assumptions of chemists based on screening data. While machine learning models using molecular properties or calculated 3D structures enable quantitative data evaluation, costly quantum chemical calculations are often required. In contrast, readily available binary fingerprint descriptors are timeand cost-efficient, but their predictive performance remains insufficient. Here, we describe a machine learning model based on fragment descriptors, which are fine-tuned for asymmetric catalysis and represent cyclic or polyaromatic hydrocarbons, enabling robust and efficient virtual screening. Using training data with only moderate selectivities, we designed theoretically and validated experimentally new catalysts showing higher selectivities in a challenging asymmetric tetrahydropyran synthesis.

show abstract

Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

Zhao

Zhang

et al. 2021

Angew Chem Int Ed

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The enantioselective aza-Diels-Alder reaction is efficient for constructing chiral tetrahydropyridines,b ut the catalytic asymmetric aza-Diels-Alder reaction of ketimines with unactivated dienes is still ac hallenging topic.H erein, guided by computational screening,ahighly enantioselective aza-Diels-Alder reaction of 2-aryl-3H-indol-3-ones with unactivated dienes was realized by using aB (C 6 F 5 ) 3 /chiral phosphoric acid catalyst system under mild conditions.T he reaction has ab road scope with respect to both aza-Diels-Alder reaction partners and hence offers rapid access to an arrayo ft etrahydropyridine derivatives with pretty outcomes (up to 99 %yield, > 20:1 dr and 98:2 er). The reaction is very efficient:l owering catalyst loadings for the model reaction to 0.1 mol %, enantioselectivity is still maintained. The synthetic utility was confirmed by transformations of the products.DFT calculations provideconvincing evidence for the interpretation of stereoselection.

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Starke und sterisch begrenzte Säuren kontrollieren fünf stereogene Zentren in der katalytischen asymmetrischen Diels‐Alder‐Reaktion von Cyclohexadienonen mit Cyclopentadien

Cited by 7 publications

References 52 publications

Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

Predicting Highly Enantioselective Catalysts Using Tunable Fragment Descriptors**

Catalytic Asymmetric Aza‐Diels–Alder Reaction of Ketimines and Unactivated Dienes

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