CY6106 : Organometallic Chemistry for Organic Synthesis

Review of formalisms such as oxidation state, 18-electron rule, classes of ligands, structure and bonding. Review of reaction mechanisms, ligand substitution, oxidative addition, reductive elimination, migratory insertion, hydride elimination, transmetallation, nucelophilic and electrophilic attack on the ligands coordinated to metals.

Organo zinc and copper reagents, preparation using transmetallation, functionalized zinc and copper reagents, synthetic applications in conjugate addition and allylic and propargylic substitution reactions.Organo tin reagents, hydrostannation reaction and synthetic utility of vinylstannanes and allylstannanes in addition and substitution reactions. Organoboron and aluminium reagents, alkyl and aryl derivatives, synthesis and examples of applications in C-C bond forming reactions. Organotitanium and zirconium reagents, metallocene complexes in C-C bond forming reactions. Addition to enynes and diynes, hydrozirconation, metallocycle formation and their synthetic utility.

Metal (W, Cr, Rh, Ru, Mo) carbene complexes, Fischer, Schrock and Grubbs type carbene complexes, comparison of their stability and reactivity, reactions of Fischer carbene complexes and their synthetic utility, Dötz reaction, simple and cross metathesis reactions, ring opening, ring closing metathesis in organic synthesis, examples from macrocycles synthesis. Copper and rhodium based carbene and nitrene complexes, cyclopropanation, Rh catalysed C-H insertion and aziridination reactions including asymmetric version. Introduction to N-heterocyclic carbene metal complexes. Metal (Fe, Cr, Mo, Ni, Co, Rh) carbonyl compounds in organic synthesis. C-C bond forming. Cyclooligomerization of alkenes, enynes and alkynes, Vollhardt reaction.Carbonylation and decarbonylation reactions and hydroformylation reaction.

Metal (Fe, Pd) ene, diene and dienyl complexes, metal complexes as protecting groups, activation towards nucleophilic addition reaction and rules governing such additions, synthetic utility. p-allyl palladium, nickel and iron complexes, synthesis and their synthetic utility. Various Wacker type oxidation and cyclization reactions including asymmetric version. Metal (Co, Zr) alkyne complexes, protection of triple bond, C-C bond forming reactions such as Pauson-Khand reaction, alkyne cyclotrimerization and oligomerization reaction. Metal (Cr, Fe, Ru) arene complexes, synthesis and structure. Activation of arene nucleus and side chain. Nucleophilic substitution and addition of arene. Metal (Rh, Ir) catalyzed C-H activation reactions and their synthetic utility.

Text Books:

  1. Schlosser, M., Organometalllics in Synthesis, A manual, John Wiley, New York, 1996.
  2. Hegedus, L.S.; Transition metals in the synthesis of complex organic molecules, second edition, University Science, Book, CA, 1999.
  3. Astruc, D.; Organometallic Chemistry and Catalysis, Springer Verlag, 2007.
  4. Davies, S. G.; Organotransition metal chemistry: Applications to organic synthesis, Pergamon Press, New York, 1986.