The asymmetric imidate rearrangement: Synthesis and investigation of novel catalysts and substrates

Chapter 1. A review of the recent progress towards the palladium(II)-catalyzed asymmetric imidate rearrangement is reported. The evolution of catalysts from palladium(II)-diamine complexes to planar chiral palladacycles is reviewed. Work in this area by several authors demonstrates the broader concept of prochiral olefin activation for attack by external nucleophiles to potentially construct numerous types of molecules.; Chapter 2. The synthesis and [3,3]-rearrangement of allylic N-benzoylbenzimidates is presented. Such imidates contain a less basic imidate nitrogen than allylic N-arylbenzimidates, and were prepared to explore ways of reducing the quantity of byproducts formed during the rearrangement of allylic N-arylbenzimidates catalyzed by chiral palladium-diamine complexes. Allylic N-benzoylbenzimidates 2.14–2.19 and 2.22–2.24 were prepared in good yield. Subsequent conversion to the corresponding allylically transposed benzimides was accomplished by Pd(II)-catalysis as well as under thermal conditions.; Chapter 3, Part I. The synthesis of palladacycles containing carbonylchromium(0)-complexed arenes is reported. The promising results obtained from the catalysis of imidate rearrangements by related ferrocenyl palladacycles beseeched the investigation of these related planar chiral compounds. Palladacycles containing the planar chiral carbonylchromium(0)-complexed arenes were synthesized by Pd(0)-insertion into aryl iodide bonds. The ortho-metallation of tricarbonylchromium(0)- and monophosphine dicarbonylchromium(0)-complexed arenes directed by chiral oxazoline groups was developed. Complementary diastereoselectivity in the metallation of the latter was achieved by addition of TMEDA.; Chapter 3, Part II. Catalysis of the [3,3]-rearrangement of allylic N-arylbenzimidates by palladacycle catalysts containing carbonylchromium(0)-complexed arenes is reported. Numerous structural modifications including arene ring and chromium tripod substitution were employed to explore the optimization of these catalysts.