Rhodium-catalyzed ortho-C-H functionalization is well known in the literature. Described herein is the Xphos-supported rhodium catalysis of meta-C-H olefination of benzylsulfonic acid and phenyl acetic acid frameworks with the assistance of a para-methoxy-substituted cyano phenol as the directing group. Complete mono-selectivity is observed for both scaffolds. A wide range of olefins and functional groups attached to arene are tolerated in this protocol.

a,b-Alkenyl carboxylicacids undergo Cu II -mediated decarboxylative annulation reactions with aliphatic cyclic ketones to provides ynthetically valuable di-heterocycles.T he annulation process tolerates avariety of aliphatic ketones and heterocyclic alkenyl carboxylic acids,p roducing substituted fused furan derivatives with complete regioselectivity.T he current protocol offers as ynthetically applicable pathway to construct avariety of oligo-heterocycles through Cu-mediated single-electron transfer and decarboxylation. Notably,s ynthesis of relatively inaccessible di-heterocycles has been achieved successfully using this protocol.

We have developed a highly regio‐ and diastereoselective rhodium‐catalyzed allylic substitution of challenging alkyl‐substituted secondary allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high‐oxidation state and bench‐stable pre‐catalyst to provide a rare example of a regio‐ and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic allylic electrophiles. Finally, the configurational fluxionality of the rhodium‐allyl intermediate is exploited to develop a novel diastereoselective process for the construction of vicinal acyclic ternary/ternary stereogenic centers, in addition to a cyclic ternary/quaternary derivative.

Rhodium-catalyzed ortho-C À Hf unctionalization is well knowni nt he literature.D escribed herein is the Xphossupported rhodium catalysis of meta-C À Ho lefination of benzylsulfonic acid and phenyl acetic acid frameworks with the assistance of ap ara-methoxy-substituted cyano phenol as the directing group.Complete mono-selectivity is observed for both scaffolds.Awide range of olefins and functional groups attached to arene are tolerated in this protocol.[ + + ]T hese authors contributed equally to this work.Supportinginformation for this article can be found under: http://dx.

We have developed a highly regio‐ and diastereoselective rhodium‐catalyzed allylic substitution of challenging alkyl‐substituted secondary allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high‐oxidation state and bench‐stable pre‐catalyst to provide a rare example of a regio‐ and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic allylic electrophiles. Finally, the configurational fluxionality of the rhodium‐allyl intermediate is exploited to develop a novel diastereoselective process for the construction of vicinal acyclic ternary/ternary stereogenic centers, in addition to a cyclic ternary/quaternary derivative.