Catalytic alkene skeletal modification for the construction of fluorinated tertiary stereocenters

Abstract

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...

α-Diazo-λ3-iodanes and α-diazo sulfonium salts: the umpolung of diazo compounds

“…Indeed, Suero has shown that this method provides access to the desired fluorinated targets with high selectivity towards the branched products (51) (Scheme 15c). 37 Cyclopropenium cations 53 can also be synthesized using the same concept via the Rh-catalysed carbene addition to alkynes. The reaction seems to proceed by initial formation of cyclopropene intermediate int-XX, followed by elimination of the iodoarene moiety.…”

Catalytic Synthesis of Cyclopropenium Cations with Rh-Carbynoids

“…Our research group is focused on the development of a carbyne transfer platform in organic synthesis using tailored hypervalent iodine reagents as carbyne synthons . The catalytic activation with dirhodium carboxylate catalysts provides access to Rh-carbynoids ( int- 1 ) (Figure ), , a novel class of Rh-carbene species substituted with an ester group and a hypervalent iodine moiety as outstanding nucleofuge .…”

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

“…Suero and co-workers have reported several reactions utilizing Rh-carbenoid species generated from pseudocyclic diazomethylbenziodoxoles and dinuclear rhodium complexes. [196][197][198] For example, reactions of reagent 136 with cyclohexene 135 and various external nucleophiles in the presence of a dinuclear rhodium complex catalyst yield products 137 with a nucleophile introduced at the allylic position (Scheme 50). [196] Heteroatom nucleophiles such as halide, azide anions, or alcohols as well as carbon nucleophiles can be applied in this reaction.…”