A Metal-Ligand Cooperative Pathway for Intermolecular Oxa-Michael Additions to Unsaturated Nitriles

An unprecedented catalytic pathway for oxa‐Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru–dieneamido complex from the reaction between the Ru c...

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Vydáno v:	Angewandte Chemie International Edition Ročník 54; číslo 14; s. 4236 - 4240
Hlavní autoři:	Perdriau, Sébastien, Zijlstra, Douwe S., Heeres, Hero J., de Vries, Johannes G., Otten, Edwin
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Weinheim WILEY-VCH Verlag 27.03.2015 WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc
Vydání:	International ed. in English
Témata:	Activation Alcohols Ambient temperature Catalysis Catalysts Chemistry Chemistry, Multidisciplinary Conjugates homogeneous catalysis Ligands Michael addition Nitriles Nitriles - chemistry non-innocent ligands Pathways Physical Sciences pincer ligands Ruthenium Ruthenium - chemistry Science & Technology Unsaturated Michael addition RU N-H BOND FORMATION pincer ligands non-innocent ligands AMINE ALCOHOLS ruthenium ACTIVATED ALKENES homogeneous catalysis PINCER COMPLEXES HYDROALKOXYLATION OLEFINS CONJUGATE ADDITIONS
ISSN:	1433-7851, 1521-3773, 1521-3773
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Shrnutí:	An unprecedented catalytic pathway for oxa‐Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru–dieneamido complex from the reaction between the Ru catalyst and pentenenitrile in combination with DFT calculations supports a mechanism in which activation of the nitrile through metal–ligand cooperativity is a key step. The nitrile‐derived Ru‐N moiety is sufficiently Brønsted basic to activate the alcohol and initiate conjugate addition of the alkoxide to the α,β‐unsaturated fragment. This reaction proceeds in a concerted manner and involves a six‐membered transition state. These features allow the reaction to proceed at ambient temperature in the absence of external base. It all adds up: A novel pathway for oxa‐Michael addition to challenging β‐substituted unsaturated nitrile substrates is described based on a dearomatized ruthenium PNN pincer catalyst (see picture). Metal–ligand cooperative activation of the nitrile is key to the observed reactivity.
Bibliografie:	Dutch Ministry of Economic Affairs ark:/67375/WNG-CC8P71ZS-M ArticleID:ANIE201412110 Merck & Co NWO The authors thank the Smart Mix Program of the Dutch Ministry of Economic Affairs and the Dutch Ministry of Education, Culture, and Science, Royal DSM NV, Merck & Co and Avantium for funding of this work within the framework of the CatchBio Program. Financial support from NWO (Veni grant to E.O.) is gratefully acknowledged. Laurent Lefort and Paul Alsters (DSM) are thanked for stimulating discussions. Claudia Poloni is thanked for her help with MALDI-TOF measurements. istex:B587DD99D1E3B53235BD0372F2B0169314F984E3 Royal DSM NV Avantium Dutch Ministry of Education, Culture, and Science The authors thank the Smart Mix Program of the Dutch Ministry of Economic Affairs and the Dutch Ministry of Education, Culture, and Science, Royal DSM NV, Merck & Co and Avantium for funding of this work within the framework of the CatchBio Program. Financial support from NWO (Veni grant to E.O.) is gratefully acknowledged. Laurent Lefort and Paul Alsters (DSM) are thanked for stimulating discussions. Claudia Poloni is thanked for her help with MALDI‐TOF measurements. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.201412110