We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. We found that rhodiumcarbynoid 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.
A highly enantioselective catalytic method for the synthesis of quaternary α-fluoro derivatives of 3-oxo esters is described. The reaction uses europium (III) triflate and commercially available chiral pybox-type C2-symmetric ligand. Excellent results in terms of yields and enantioselectivities were assured using the electrophilic NFSI reagent under mild reaction conditions.
Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C( sp 2 )–C( sp 2 ) bond cleavage. The new process, that takes advantage of...
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