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()-C() bond scission in alkenes by inserting a monovalent carbon unit between both -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 intermediates able to undergo electrocyclic ring-opening, following the Woodward-Hoffmann-DePuy rules.
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| http://dx.doi.org/10.1021/jacs.9b08632 | DOI Listing |
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