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Computational studies revealed that dirhodium tetrakis(1,2,2‐triarylcyclopropanecarboxylate) (Rh₂(TPCP)₄) catalysts adopt distinctive high symmetry orientations, which are dependent on the nature of the aryl substitution pattern. The parent catalyst, Rh₂(TPCP)₄, and those with ap‐substituent at the C1 aryl, such as Rh₂(p‐BrTPCP)₄and Rh₂(p‐PhTPCP)₄, adopt aC₂‐symmetric structure. Rh₂(3,5‐di(p‐^tBuC₆H₄)TPCP)₄, 3,5‐disubstituted at the C1 aryl, adopts aD₂‐symmetric structure, whereas catalysts with ano‐substituent at the C1 aryl, such as Rh₂(o‐Cl‐5‐BrTPCP)_4,adopt aC₄‐symmetric structure.

Regio‐ and stereoselective distal allylic/benzylic C−H functionalization of allyl and benzyl silyl ethers was achieved using rhodium(II) carbenes derived from N‐sulfonyltriazoles and aryldiazoacetates as carbene precursors. The bulky rhodium carbenes led to highly site‐selective functionalization of less activated allylic and benzylic C−H bonds even in the presence of electronically preferred C−H bonds located α to oxygen. The dirhodium catalyst Rh₂(S‐NTTL)₄is the most effective chiral catalyst for triazole‐derived carbene transformations, whereas Rh₂(S‐TPPTTL)₄works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of δ‐functionalized allyl silyl ethers with high diastereo‐ and enantioselectivity. The utility of the present method was demonstrated by its application to the synthesis of a 3,4‐disubstitutedl‐proline scaffold.