Organozinc and organomercury derivatives. Organotransition metal derivatives. Ligand exchange, oxidative addition, reductive elimination, intramolecular insertion, β-elimination, nucleophilic attack to unsaturated organic ligands. Reactions of σ-alkyl and π alkene, alkyne, allyl, arene complexes. Reactivity of Fischer and Schrock metal carbene complexes.
L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books
J. Hartwig, Organotransition Metal Chemistry – From Bonding to Catalysis, University Science Books
Ch. Elschenbroich, A. Salzer, Organometallics, Cap. 12-15, 17, VCH Publishers
J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke, Principles and Applications of Organotransition Metal Chemistry, Cap. 1-2, 4-6, 16-20, University Science Books
M. Beller, C. Bolm, Transition Metals for Organic Synthesis, Vol. 1, Cap. 2.7, 2.10, 2.11, 2.13, 2.14, 2.15, 3.1, 3.2, 3.12, 3.13, Wiley-VCH
Learning Objectives
Knowledge of the basic concepts of the chemistry of organotransition metal compounds. Methods and procedures in the use of organotransition metal compounds.
Prerequisites
Courses required: none
Courses recommended: none
Teaching Methods
Hours of frontal teaching: 48
Type of Assessment
Final oral examination. At least 8 sessions are programmed, in January, February, June, July, and September.
Course program
Properties of the M-C bond. Stability, decomposition and manipulation of organometallic derivatives. Purification and analysis of organometallic derivatives. Organozinc derivatives. Preparation. Reactions with acyl halides and ketones. Noyori reaction. Reformatskii reaction. Simmons-Smith cyclopropanation. Enantioselective cyclopropanations. Takai-Lombardo olefination. Organocadmium derivatives: preparation, use. Organomercury derivatives: preparation, structure, reactivity. Use of organomercurials. Toxicity of Hg salts and compounds. The chemistry of organotransition metal derivatives. Variety of ligands, metals, oxidation states, coordination modes. Conventions and formalisms. 18 electron rule and the electron calculation. Back-bonding: influence on structure and reactivity. Coordinatively saturation and unsaturation. Metal carbonyl complexes. Classes of complexes with respect to the 18 electron rule. Polymetallic complexes: M-M bond order calculation. Reactions of organotransition metal complexes. Ligand exchange: associative and dissociative mechanisms. Oxidative addition and reductive elimination. Polar, apolar and unsaturated reagents and their mechanisms. Formation of C-H and C-C bonds by reductive elimination. Intramolecular or migratory insertion. σ-Alkyl complexes: β-elimination. Preparation or formation of σ-organyl complexes. Organocopper derivatives: preparation and variety. Gilman cuprates, higher order cuprates, heterocuprates, cyanocuprates. Coupling reactions with organohalides, epoxides, acyl halides. Conjugate addition to α,β-unsaturated carbonyl derivatives. σ-Organyl Pd complexes: “in situ” formation by oxidative addition. Sources of Pd(0). Phosphine ligands. Heck reaction. CO insertion. σ-Alkyl complexes from hydrometallation: hydropalladation and hydrozirconation. Cycloisomerization of enynes. Pd-catalyzed domino reactions. Use of σ complexes of Zr. Cross-coupling reactions via transmetallation. Available organometallics for Pd-catalyzed cross-coupling reactions. Kumada, Negishi, Stille, Suzuki reactions. Coupling-carbonylation reactions. Sonogashira reaction. Cu(I) catalyzed cycloaddition of azides with terminal alkynes. C-N and C-O bond formation. Buchwald-Hartwig reaction. Narasaka-Heck reaction. Complexes with π ligands: bonding. Nucleophilic addition to metal bound polyenes: Davies-Green-Mingos rules. Organotransition metal complexes used as protecting groups and stabilizing moieties. Reactivity of alkene complexes. The Wacker process. Insertion of CO and electron poor alkenes in σ-alkyl intermediate complexes. Nitrogen heterocycle formation via domino and one-pot Pd-catalyzed aminocarbonylation and carboamination of alkene Pd(II) and amido Pd(II) complexes. Pd(0) and Cu(I) catalyzed diamination of conjugated dienes and trienes and of alkenes with diaziridinones. Reactions catalyzed by gold complexes. Activation of alkynes and alkenes: protodemetallation, carbenoid behavior. Au(I) catalyzed hydroamination reactions of alkenes, alkynes and allenes. Reactions of zirconacyclopropanes and titanacyclopropanes. Zirconocene. Dimerization of alkenes and alkynes and cycloisomerization of enynes. Carbomagnesiation of alkenes catalyzed by zirconocene. Kulinkovich reaction. Co-alkyne complexes: structure. Nicholas reaction. Pauson-Khand reaction. Cyclotrimerization of alkynes. Variants with alkynes, nitriles, imines, isocyanates. π-Allyl complexes: bonding, structure, preparation. Reactivity of π-allyl complexes. Nucleophilic attack. Vinyloxiranes. Combination with nucleophilic addition to π-alkene complexes: diacetoxylation and chloroacetoxylation of dienes. Chemistry of TMM: [3+2] cycloadditions. Trost method and Pd and Ni catalyzed methylenecyclopropanes ring opening. Metal arene complexes: synthesis and properties. Reactivity of (arene)Cr(CO)3 complexes: nucleophilic substitution, addition/oxidation, addition/protonation. Bulkiness of Cr(CO)3: diastereoselectivity. Chirality of ortho- and meta-disubstituted arene complexes: application in enantioselective symtheses. The three classes of metal carbene complexes. Fischer metal carbenes: preparation and properties. Dötz and Hegedus reactions. Unstabilized electrophilic carbenes: cyclopropanation. Metal nitrene complexes: aziridination of alkenes, C-H bond insertion. Schrock metal carbene complexes. Olefination: Tebbe reagent, titanacyclobutanes, Petasis reaction. Alkene metathesis: the Chauvin mechanism. Typologies of alkene metatheses: CM, RCM, ROM, ROMP, domino reactions. Catalysts for metathesis: Schrock, Grubbs I and II generation, Herrmann, Hoveyda-Grubbs, supported, chiral catalysts. Metathesis of enynes. Metathesis of alkynes.