Cyanoesterification of Norbornenes Catalyzed by Palladium: Facile Synthetic Methodology to Introduce Cyano and Ester Functionalities via Direct Carbon—Carbon Bond Cleavage of Cyanoformates.

Abstract

Bridged compounds Q 0060 Cyanoesterification of Norbornenes Catalyzed by Palladium: Facile Synthetic Methodology to Introduce Cyano and Ester Functionalities via Direct Carbon--Carbon Bond Cleavage of Cyanoformates. -A diversity of cyanoformates (II) is successfully added towards norbornene, norbornadiene as well as its benzo analogues to afford the corresponding exo,exo-adducts in moderate to good yields. The reaction is strongly influenced by steric factors. -(NISHIHARA*, Y.; INOUE, Y.; IZAWA, S.; MIYASAKA, M.; TANEMURA, K.; NAKAJIMA, K.; TAKAGI, K.; Tetrahedron 62 (2006) 42, 9872-9882; Dep. Chem., Grad. Sch. Nat. Sci. Technol., Okayama Univ., Okayama 700, Japan; Eng.) -Mischke 05-063

Catalytic C–C Bond Activations via Oxidative Addition to Transition Metals

“…Besides the shown examples with alkyne acceptors, alkenes were found to engage in cyanoesterification and cyanocarbamoylation reactions. For instance, Nishihara reported intermolecular palladium­(II)-catalyzed cyanoesterifications of strained reactive alkenes 610 such as norbornene or norbornadiene (Scheme ). − Modification of the ester moiety of 609 with a variety of alkyl groups is tolerated and the functionalized norbornene derivatives 613 are obtained in moderate to high yields with high exo -selectivity. However, the process is limited to activated norbornenes and other less reactive olefin acceptors fail.…”