Catalytic Cleavage of C(sp 2)–C(sp 2) Bonds with Rh-Carbynoids

We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C­(sp 2)–C­(sp 2) bond scission in alkenes by inserting a monovalent carbon unit between both sp 2-hybridized carbons. This skel...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 141; no. 39; pp. 15509 - 15514
Main Authors Wang, Zhaofeng, Jiang, Liyin, Sarró, Pau, Suero, Marcos G
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.10.2019
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
SOLVOLYSIS
ACTIVATION
COUPLING REACTIONS
COMPLEXES
DECOMPOSITION
CHEMISTRY
CARBON-CARBON
DIAZO-COMPOUNDS
CHROMIUM
ATOM
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Summary:We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodium-carbynoid species provoke C­(sp 2)–C­(sp 2) bond scission in alkenes by inserting a monovalent carbon unit between both sp 2-hybridized carbons. This skeletal remodeling process accesses synthetically useful allyl cation intermediates that conduct to valuable allylic building blocks upon nucleophile attack. Our results rely on the formation of cyclopropyl-I(III) intermediates able to undergo electrocyclic ring-opening, following the Woodward–Hoffmann–DePuy rules.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b08632