Enantiomerically enriched trans-diols from alkenes in one pot: a multicatalyst approach

Hrdina, Radim; Müller, Christian; Wende, Raffael C.; Wanka, Lukas; Schreiner, Peter R.

doi:10.1039/c2cc17435a

Cited by 28 publications

(40 citation statements)

References 18 publications

(23 reference statements)

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“…[197] Die Bedeutung intramolekularer LD für enantioselektive organokatalytische Reaktionen wurde kürzlich demonstriert, [198] und es wurde gezeigt, dass es sogar in kurzen Peptiden mit vielen polaren Bindungen für ionische Wechselwirkungen und Wasserstoffbrücken immer noch einen signifikanten Effekt der LD gibt, entweder durch die Bildung einer bestimmten Katalysatorstruktur oder durch deren Beitrag zur Substraterkennung. [199] Dieser Ansatz war wichtig bei der Nutzung unpolarer Reaktanten für organokatalytische Reaktionssequenzen, [200] die in Gegenwart kleiner PeptidMultikatalysatoren als Modelle für kleine Enzyme zu enantiomerenreinen Produkten führen. [201] Die Verbindung zwischen der Katalyse mithilfe kleiner Moleküle und der enzymatischen Katalyse in der asymmetrischen Katalyse wurde auf der Basis attraktiver nichtkovalenter Wechselwirkungen hergestellt.…”

Section: London'sche Dispersionunclassified

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

2015

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Die London’sche Dispersion, die den attraktiven Teil des Van‐der‐Waals‐Potentials beschreibt, wurde lange als Element struktureller Stabilität in der molekularen Chemie unterschätzt. Als solches beeinflusst sie auch entscheidend die chemische Reaktivität und Katalyse. Ihre Vernachlässigung ist auf die Annahme zurückzuführen, dass die Dispersionswechselwirkung schwach sei, was nur für eine einzelne paarweise Wechselwirkung zweier Atome stimmt. Für Strukturen zunehmender Größe kann die gesamte Dispersionsstabilisierung mehrere zehn kcal mol−1 betragen. Dieser Aufsatz soll die Wichtigkeit inter‐ und intramolekularer Dispersion anhand von Beispielen für die erste Vollperiode verdeutlichen. Die Synergie aus Experiment und Theorie hat ein Niveau erreicht, auf dem Dispersionseffekte sehr genau verstanden werden können. Als Konsequenz daraus werden wir wohl unser Verständnis bezüglich sterischer Hinderung und stereoelektronischer Effekte überdenken müssen. Die Quantifizierung von Dispersionsenergiedonoren wird unsere Fähigkeiten verbessern, komplexe molekulare Strukturen und Katalysatoren zu entwickeln.

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Section: London'sche Dispersionunclassified

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

2015

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“…Thereby, the monoacetylated products (R,R)-284 formed with good enantioselectivities (up to 74% ee for (R,R)-284a) leading to S-values of up to 48 (at 57% conversion). 113 Indeed, 285 is not a multicatalyst in that sense. Referring to the terminology of Fogg and dos Santos 4 this example can be labelled as assisted tandem reaction.…”

Section: Miscellaneous Examples Of Oligopeptide Catalyzed Reactionsmentioning

confidence: 99%

“…Starting from cyclohexene (281a) this three-step reaction sequence furnished (S,S)-283a and (R,R)-284a with >99% ee and 73% ee, respectively, corresponding to an excellent S-value of 45 (an experiment at preparative scale gave a S-value of 26; Scheme 45). 113 …”

Section: Miscellaneous Examples Of Oligopeptide Catalyzed Reactionsmentioning

confidence: 99%

“…113 Preparing the bisulfate salt 285 as an analogue of 280 (due to its acid lability the Boc-protecting group was exchanged by an acetyl group) allowed the epoxide opening (Scheme 44). Addition of Hünig's base in the next step releases the acylation catalyst, thus enables the subsequent kinetic resolution of (±)-283.…”

Section: Miscellaneous Examples Of Oligopeptide Catalyzed Reactionsmentioning

confidence: 99%

“…113 Multicatalyst 279 in conjunction with hydrazinium sulfate (280) enabled the synthesis of enantiomerically enriched trans-1,2-alkanediols (S,S)-283 and monoacetylated diols (R,R)-284 employing simple symmetrical alkenes 281, hydrogen peroxide, water, and acetic anhydride. Hence, the epoxidation of alkenes 281 catalyzed by the aspartate moiety 114 proceeds via intramolecular anhydride formation using N,N′-diisopropyl carbodiimide (DIC) as dehydrating agent.…”

Section: Multicatalyst Approachesmentioning

confidence: 99%

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Evolution of asymmetric organocatalysis: multi- and retrocatalysis

2012

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The evolution of organocatalysis led to various valuable approaches, such as multicomponent as well as domino and tandem reactions. Recently, organomulticatalysis, i.e., the modular combination of distinct organocatalysts enabling consecutive reactions to be performed in one pot, has become a powerful tool in organic synthesis. It allows the construction of complex molecules from simple and readily available starting materials, thereby maximizing reaction efficiency and sustainability. A logical extension of conventional multicatalysis is a multicatalyst, i.e., a catalyst backbone equipped with independent, orthogonally reactive catalytic moieties. Herein we highlight the impressive advantages of asymmetric organomulticatalysis, examine its development, and present detailed reactions based on the catalyst classes employed, ranging from the very beginnings to the latest multicatalyst systems. R. C. Wende was born inRosenberg (Olesno), Poland, in 1984. He studied chemistry at the Justus-Liebig University, Giessen, where he obtained his B. Sc. degree in 2008 and his M. Sc. degree in 2010. Currently he is working on his PhD under the supervision of P. R. Schreiner. His research focuses on the development of novel synthetic oligopeptide and thiourea organocatalysts for multicatalysis reactions.

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Kinetic Resolution and Desymmetrization of Alcohols and Amines by Nonenzymatic, Enantioselective Acylation

et al. 2020

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Enantiomerically pure alcohols and amines are ubiquitous throughout Nature and are found within numerous biologically active compounds. This chapter provides a comprehensive overview of strategies for the nonenzymatic acylative kinetic resolution and desymmetrization of alcohols and amines, which have emerged as powerful methods for the preparation of a range of enantiomerically enriched alcohol and amine derivatives. The use of both stoichiometric chiral acylating agents and the use of small‐molecule catalysts for such processes is discussed. The chapter provides an overview of the variety of substrates that can be effectively resolved using the range of enantioselective acylation methods available. Key mechanistic considerations within each class of acylation and the origin of stereoselectivity are also discussed.

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Enantiomerically enriched trans-diols from alkenes in one pot: a multicatalyst approach

Abstract: Multicatalysts consisting of non-natural oligopeptides with distinctly different catalytic moieties create molecular complexity in a multistep one-pot sequence starting from simple alkenes yielding highly enantiomerically enriched trans-diols.

Cited by 28 publications

References 18 publications

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

Evolution of asymmetric organocatalysis: multi- and retrocatalysis

Kinetic Resolution and Desymmetrization of Alcohols and Amines by Nonenzymatic, Enantioselective Acylation

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