A Rhodium Thing

Ever since my first encounter with aldehyde C-H insertion by rhodium, I have been intrigued by the possibilities of the acylorganometallic intermediates. In Org. Lett. a nice formal [4+2] cycloaddition appeared utilizing ortho-vinyl benazaldehydes and olefins or alkynes. The reaction proceeds via C-H insertion to form an acylrhodium followed by a migratory insertion to produce a rhodacylopentene. This reacts with an alkene to form the product shown. Chiral ferrocenyl phosphine ligands afforded at least modest level of enationselectivity. If alkynes were utilized, napthol products were produced. Although most yields and selectivities were modest, it is an interesting transformation. It seems to be limited in scope. Without the arene ring cyclization did not take place. Instead the acylrhodium simply reacts with the olefin in a reductive Heck-type process to afford an acyclic ketone.

Ken Tanaka, Daiki Hojo, Takeaki Shoji, Yuji Hagiwara, and Masao Hirano, DOI: 10.1021/ol0704587