Application of Transition Metal Catalysts in Organic Synthesis

ISBN-13: 9783540655503 / Angielski / Miękka / 1999 / 335 str.

L. Brandsma; S. F. Vasilevsky; H. D. Verkuijsse

Opis

Homogeneous catalysis is an important strategy for the synthesis of high-valued chemicals. L. Brandsma has carefully selected and checked the experimental procedures illustrating the catalytic use of copper, nickel, and palladium compounds in organic synthesis. All procedures are on a preparative scale, make economic use of solvents and catalysts, avoid toxic substances and have high yields.

Spis treści

1 Catalysts, Ligands and Reagents.- 1.1 Catalysts.- 1.1.1 Copper Halides.- 1.1.1.1 Solubilization of Copper(I) Halides.- 1.1.2 Nickel Catalysts.- 1.1.2.1 Nickel(II)bromide·bis(triphenylphosphane).- 1.1.2.2 Nickel(II)chloride·bis(triphenylphosphane).- 1.1.2.3 Nickel(II)chloride·1,3-bis(diphenylphosphino) propane.- 1.1.2.4 Nickel(II)chloride·1,2-bis(diphenylphosphino)ethane.- 1.1.2.5 Nickel(II)chloride·1,4-bis(diphenylphosphino)butane.- 1.1.2.6 Nickel(II)chloride·1,1?-bis(diphenylphosphino)ferrocene.- 1.1.2.7 Nickel(II)bromide·1,1?-bis(diphenylphosphino)ferrocene.- 1.1.2.8 trans-Chloro(1-naphthyl)bis(triphenylphosphane)nickel.- 1.1.2.9 trans-Bromo(1-naphthyl)bis(triphenylphosphane)nickel and trans-Bromo(phenyl)bis(triphenyl-phosphane)nickel.- 1.1.3 Palladium Catalysts.- 1.1.3.1 Palladium(II)chloride·bis(acetonitrile).- 1.1.3.2 Palladium(II)chloride·bis(benzonitrile).- 1.1.3.3 Palladium(II)chloride·bis(triphenylphosphane).- 1.1.3.4 Palladium(II)chloride·1,4-bis(diphenylphosphino)butane.- 1.1.3.5 Palladium(II)chloride·1,1?-bis(diphenylphosphino)ferrocene.- 1.1.3.6 Tetrakis(triphenylphosphane)palladium(0).- 1.1.3.7 Tris(dibenzylideneacetone)dipalladium(0)·chloroform.- 1.2 Ligands.- 1.2.1 1,n-Bis(diphenylphosphino)alkanes (n= 2,3,4).- 1.2.1.1 1,2-Bis(diphenylphosphino)ethane.- 1.2.1.2 1,3-Bis(diphenylphosphino)propane.- 1.2.1.3 1,4-Bis(diphenylphosphino)butane.- 1.2.2 1,1?-Bis(diphenylphosphino)ferrocene.- 1.2.3 Triarylphosphanes and Tri(hetaryl)phosphanes.- 1.3 Organometallic Reagents.- 1.3.1 Preparation of Grignard Reagents from Mg and Organic Halides.- 1.3.2 Preparation of Organomagnesium and Organozinc Halides by Lithium-Magnesium or Lithium-Zinc Exchange.- 1.3.3 Preparation of Organoaluminum Intermediates.- 1.3.4 Preparation of Organoboron and Organotin Intermediates.- 1.3.4.1 2-Thiopheneboronic Acid.- 1.3.4.2 2-Furanboronic Acid.- 1.3.4.3 4-(Fluorophenyl)boronic Acid.- 1.3.4.4 (2-Methoxyphenyl)boronic Acid.- 1.3.4.5 2-Tributylstannylfuran.- 1.3.4.6 1-Methyl-2-tributylstannylpyrrole.- 1.3.4.7 4-Methyl-2-tributylstannylthiazole.- 1.3.4.8 Stannylation of Ethyl Vinyl Ether.- 2 Procedures for the Preparation of Halogen Compounds.- 2.1 sp-Halides.- 2.1.1 1-Bromo-1-propyne and 1-Bromo-1-butyne.- 2.1.2 1-Bromo-1-pentyne and 1-Bromo-1-hexyne.- 2.1.3 Other 1-Bromo-1-alkynes.- 2.1.4 Reaction of Alkynyllithium with Iodine in Organic Solvents.- 2.1.5 Preparation of Iodoacetylenes from Lithiated Acetylenes and Iodine in Liquid Ammonia.- 2.2 Aryl and Hetaryl Halides.- 2.2.1 2-Bromothiophene.- 2.2.2 2,5-Dibromothiophene.- 2.2.3 2,3,5-Tribromothiophene.- 2.2.4 3-Bromothiophene.- 2.2.5 2,3-Dibromothiophene.- 2.2.6 3,4-Dibromothiophene.- 2.2.7 2,4-Dibromothiophene.- 2.2.8 2-Bromofuran.- 2.2.9 2,3-Dibromofuran.- 2.2.10 3-Bromofuran.- 2.2.11 2,5-Dibromofuran.- 2.2.12 2-Iodothiophene.- 2.2.13 3-Iodothiophene.- 2.2.14 2-Iodofuran.- 2.2.15 2-Iodo-1-methylimidazole.- 2.2.16 2-Iodo-1-methylpyrrole.- 2.2.17 1-Bromo-4-iodobenzene.- 2.2.18 3-Bromoquinoline.- 2.3 Olefinic, Cycloolefinic and Allenic Halides.- 2.3.1 1-Bromo-2-methylpropene.- 2.3.2 ?-Bromostyrene.- 2.3.3 2-Bromo-1-ethoxyethene.- 2.3.4 3-Bromo-5,6-dihydro-4H-pyran.- 2.3.5 1-Bromocyclooctene.- 2.3.6 1-Chlorocyclohexene.- 2.3.7 Z-1,4-Dibromo-2-butene and 1-Bromo-1,3-butadiene.- 2.3.8 E-1,4-Dibromo-2-butene and 1-Bromo-1,3-butadiene.- 2.3.9 2-Bromo-1,3-butadiene.- 2.3.10 1-Bromo-3-methyl-1,2-butadiene.- 2.3.11 1-Bromo-1,2-butadiene.- 2.3.12 1-Bromocyclohexene.- 2.3.13 1-Bromocyclopentene.- 2.3.14 E-1-Bromo-1-octene.- 2.3.15 E-1-Iodo-1-heptene.- 3 Cross-Coupling Between 1-Alkynes and 1-Bromoalkynes.- 3.1 Introduction.- Table 1.- 3.2 Scope and Limitations.- 3.3 Relative Reactivities of the Acetylene and the Bromoacetylene.- Table 2.- 3.4 Conditions for the Coupling.- 3.5 Choice of the Reaction Partners.- 3.6 Side Reactions.- 3.7 Experimental Part.- 3.7.1 General Remarks and Some Observations.- 3.7.2 Performance of Cu-Catalyzed Cadiot-Chodkiewicz Couplings.- 3.7.3 Typical Procedure for the Pd/Cu-Catalyzed Cross Coupling Between 1-Bromo-1-alkynes and Acetylenes.- 4 Copper-Catalyzed Aminoalkylation of Acetylenes.- 4.1 Introduction, Scope and Mechanism.- 4.2 Experimental Part.- 4.2.1 Reaction of Acetylenic Alcohols with Dimethylaminomethanol.- 4.2.2 General Procedure for the Mannich Reaction of Acetylenes Without an OH-Function.- 4.2.3 Mannich Reactions with Gaseous Acetylenes.- 5 Copper(I)-Halide-Catalyzed Oxidative Coupling of Acetylenes.- 5.1 Introduction.- 5.2 Methods, Scope and Limitations.- 5.3 About the Mechanism.- 5.4 Experimental Part.- 5.4.1 Oxidative Coupling of Propargyl Alcohol Catalyzed by Copper(I)Chloride in Aqueous Medium.- 5.4.2 Oxidative Couplings Catalyzed by Copper(I)Chloride·TMEDA in Acetone.- 5.4.2.1 Oxidative Coupling of Methyl Propargyl Ether.- 5.4.2.2 Oxidative Coupling of 3-Butyn-2-ol.- 5.4.2.3 Oxidative Coupling of 2-Methyl-3-butyn-2-ol.- 5.4.2.4 Oxidative Coupling of 3-Butyn-1-ol.- 5.4.2.5 Oxidative Coupling of 1-Methoxy-1-buten-3-yne.- 5.4.2.6 Oxidative Coupling of Arylacetylenes.- 5.4.2.7 Oxidative Coupling of Propargyl Alcohol.- 5.4.3 Oxidative Couplings Catalyzed by Copper(I)Chloride·TMEDA in N,N-Dimethylformamide.- 5.4.3.1 Oxidative Coupling of 1,1-Diethoxy-2-propyne.- 5.4.3.2 Oxidative Coupling of Ethyl Propargyl Sulfide.- 5.4.4 Oxidative Couplings Catalyzed by Copper(I)Chloride in Pyridine.- 5.4.4.1 Oxidative Coupling of 4-Butyn-1-ol.- 5.4.4.2 Oxidative Coupling of 2-Ethynylpyridine.- 5.4.5 Oxidative Couplings Catalyzed by Copper(I)Chloride and Diazabicycloundecene.- 5.4.5.1 Oxidative Coupling of 1-Butyne.- 5.4.5.2 Oxidative Coupling of 2-Ethynyl-1-methylpyrrole.- 5.4.5.3 Oxidative Coupling of t-Butylacetylene.- 5.4.6 Oxidative Coupling of Trimethylsilylacetylene.- 5.4.7 Oxidative Coupling of the HCl-Salt of 3-Amino-3-methyl-1-butyne.- 5.5 Summary of Experimental Conditions for Oxidative Couplings.- Table 3.- 6 Copper(I)-Halide-Catalyzed Substitution of sp2-Halogen by Alkoxide.- 6.1 Introduction.- 6.2 Scope and Limitations of the Copper-Catalyzed Nucleophilic Substitution of sp2-Halogen by Alkoxy Groups.- Table 4.- 6.3 Mechanistic Investigations.- 6.4 Reaction Conditions.- 6.4.1 Solvent and Reaction Temperature.- 6.4.2 The Catalyst.- 6.5 Differences in the Reactivities of the Various sp2-Halides.- 6.6 Side Reactions.- 6.7 Applications.- 6.8 Experimental Part.- 6.8.1 General.- 6.8.1.1 Reaction Conditions and Observations.- 6.8.1.2 Apparatus and Equipment.- 6.8.2 Methoxylation.- 6.8.2.1 2-Methoxythiophene.- 6.8.2.2 3-Methoxythiophene.- 6.8.2.3 3-Methoxypyridine.- 6.8.2.4 3,4-Dimethoxythiophene.- 6.8.2.5 1-Methoxycyclooctene.- 6.8.3 Other Alkoxylations.- 6.8.3.1 2-Ethoxy thiophene.- 6.8.3.2 3-Ethoxythiophene.- 6.8.3.3 3-Isopropoxythiophene.- 6.8.3.4 2-(2?Dimethylaminoethoxy)furan.- 6.8.3.5 2-(2?Dimethylaminoethoxy)thiophene.- 6.8.3.6 1-(2?Dimethylaminoethoxy)cyclooctene.- 6.8.3.7 2-(2?Methoxyethoxy)thiophene.- 6.8.3.8 1,4-Bis(2,2,2-trifluoroethoxy)benzene.- 7 Copper-Catalyzed Carbon-Carbon Bond Formation by 1,1- and 1,3-Substitution Reactions.- 7.1 Introduction.- 7.2 Displacement of Halide, Tosylate and Acetate in Saturated Compounds.- 7.3 Ring Opening of Saturated Epoxides.- 7.4 Reactions with Allylic Substrates.- 7.5 Reactions with Propargylic and Allenic Substrates.- 7.6 About the Mechanism of Copper Catalyzed Substitutions.- 7.7 Experimental Section.- 7.7.1 Alkylation Reactions with Halides and Tosylates.- 7.7.1.1 2,2,7,7-Tetramethyloctane.- 7.7.1.2 5,5-Dimethylhexan-1-ol.- 7.7.1.3 Selective Substitution of Bromine in 1-Bromo-4-chlorobutane.- 7.7.1.4 Selective Mono-Substitutions with 1,n-Dibromoalkanes.- 7.7.1.5 Displacement of Tosylate in Alkyl Tosylates.- 7.7.1.6 Neopentylbenzene.- 7.7.1.7 Benzyl-Aryl Couplings.- 7.7.1.8 t-Butylallene.- 7.7.1.9 Coupling Between Propargyl Alcohol and Propargyl Chloride in Aqueous Solution.- 7.7.1.10 Couplings Between Acetylenic Grignard Reagents and Allyl Bromide or Propargyl Bromide.- 7.7.1.11 Reactions of Grignard Reagents with Propargylic Tosylates.- 7.7.2 Substitutions with Cyclic and Non-Cyclic Ethers.- 7.7.2.1 Preparation of 1-Alkenyl Ethers from Grignard Reagents and 1,1-Diethoxy-2-propene.- 7.7.2.2 Reaction of Phenylmagnesium Bromide with Cyclohexene Oxide.- 7.7.2.3 Preparation of Allenic Ethers from Propargylaldehyde Diethylacetal and Grignard Reagents.- 7.7.2.4 Cyclohexylallene.- 7.7.2.5 Preparation of Allenic Alcohols from Acetylenic Epoxides and Grignard Reagents.- 7.7.2.6 Reaction of 2-Ethynyltetrahydropyran with a Grignard Reagent.- 7.7.2.7 3-Cyclopentyl-1-propyne.- Table 5.- Table 6.- 8 Nickel Catalyzed Iodo-Dechlorination and Iodo-Debromination of sp2-Halides.- 8.1 Introduction.- 8.2 Scope and Limitations.- 8.3 Mechanistic Investigations.- 8.4 Side Reactions.- 8.5 Experimental Procedures.- 8.5.1 Conversion of 1-Bromocyclooctene into 1-Iodocyclooctene.- 8.5.2 1-Iodocyclohexene from 1-Chlorocyclohexene (Zn/NiBr2).- 8.5.3 1-Iodocyclohexene from 1-Chlorocyclohexene (Ni(COD)2 ).- 8.6 Conclusions from our Investigations.- 9 Nickel- and Palladium-Catalyzed Cyanation of sp2-Halides and sp2-Triflates.- 9.1 Introduction.- 9.2 Scope and Limitations.- Table 7.- 9.3 Mechanism of the Nickel Catalyzed Cyanation.- 9.4 Methods of Performing Nickel Catalyzed Cyanations.- 9.5 Relative Reactivities of sp2-Halides.- 9.6 Side Reactions.- 9.7 Catalysis by Palladium Compounds.- 9.8 Experimental Part.- 9.8.1 General Procedure for the Nickel Catalyzed Cyanation of sp2-Halides in Absolute Ethanol.- 9.8.2 General Procedures for Cyanations Proceeding Under the Influence of a Ni0-Catalyst Generated by Reducing a NiII- Precatalyst with Zinc Powder.- 9.8.2.1 Cyanation of p-Chlorobenzotrifluoride.- 9.8.2.2 Cyanation of 1-Bromocyclooctene.- 9.8.3 Palladium-Catalyzed Cyanation of Aryl Iodides.- 9.8.4 Palladium-Catalyzed Cyano-Debromination of Bromoolefins.- 10 Couplings of Acetylenes with sp2-Halides.- 10.1 Introduction.- 10.2 Mechanistic Considerations.- 10.3 Scope and Limitations.- Table 8.- 10.4 Relative Rates of Coupling.- 10.5 Regiochemistry and Stereochemistry.- 10.6 Synthetic Applications of the Cross-Coupling Reactions with Acetylenes.- 10.6.1 Simple Applications of the Cross-Coupling.- 10.6.2 Synthesis of Structurally Interesting Acetylenic Compounds.- 10.6.3 Coupling Followed by Cyclization.- 10.6.4 Synthesis of Biologically Interesting Compounds.- 10.6.5 Special Methods.- 10.7 Practical Aspects of the Coupling Reactions.- 10.7.1 Performance of the Reactions and Isolation of the Products.- 10.7.2 Choice of the Solvent and Catalysts for Coupling Reactions.- 10.8 Experimental Section.- 10.8.1 Pd/Cu-Catalyzed Cross Couplings of Acetylenic Compounds with Aliphatic sp2-Halides Using Diethylamine as a Solvent.- 10.8.1.1 4-Penten-2-yn-1-ol.- 10.8.1.2 4-Methyl-4-penten-2-yn-1-ol.- 10.8.1.3 1-Nonen-3-yne.- 10.8.1.4 2-Methyl-6-trimethylsilylhexa-2,3-dien-5-yne.- 10.8.1.5 6-Ethoxy-2-methylhex-5-en-3-yn-2-ol.- 10.8.1.6 6-Ethoxyhex-5-en-3-yn-2-ol.- 10.8.1.7 2,5-Dimethylhex-5-en-3-yn-2-ol.- 10.8.1.8 2,6-Dimethylhep-5-en-3-yn-2-ol.- 10.8.1.9 5-Trimethylsilylethynyl-2,3-dihydro-4H-pyran.- 10.8.1.10 6-Chloro-2-methylhex-5-en-3-yn-2-ol.- 10.8.1.11 1-Chlorodec-1-en-3-yne.- 10.8.1.12 2-Chlorooct-1-en-3-yne.- 10.8.1.13 Other Cross Couplings, Using Similar Conditions.- 10.8.2 Pd/Cu-Catalyzed Couplings of Acetylene with Aryl and Hetaryl Halides.- 10.8.2.1 1,2-Bis(4-acetylphenyl)ethyne.- 10.8.2.2 Bis(4-methylphenyl)ethyne.- 10.8.2.3 Di(2-pyridyl)ethyne.- 10.8.2.4 Di(2-thienyl)ethyne.- 10.8.2.5 Di(3-thienyl)ethyne.- 10.8.2.6 Bis(1-methylimidazol-2-yl)ethyne.- 10.8.3 Pd/Cu-Catalyzed Couplings of Acetylenic Compounds with Aryl and Hetaryl Halides Using Diethylamide as a Solvent.- 10.8.3.1 1-Nitro-4-(trimethylsilylethynyl)benzene.- 10.8.3.2 3-Bromo-4-trimethylsilylethynylthiophene.- 10.8.3.3 2-(Penta-1,3-diynyl)thiophene.- 10.8.4 Pd/Cu-Catalyzed Couplings of Acetylenic Compounds with Aryl and Hetaryl Halide Using Triethylamine as a Solvent.- 10.8.4.1 2-(Trimethylsilylethynyl)thiophene.- 10.8.4.2 2-(Trimethylsilylethynyl)furan.- 10.8.4.3 3-(Trimethylsilylethynyl)pyridine.- 10.8.4.4 3-(4-Nitrophenyl)prop-2-yn-1-ol.- 10.8.4.5 4-(Trimethylsilylethynyl)acetophenone.- 10.8.4.6 2-Methyl-4-(4-methoxyphenyl)but-3-yn-2-ol.- 10.8.4.7 3-(2-Thienyl)prop-2-yn-1-ol.- 10.8.4.8 2-Methyl 4-(2-methoxyphenyl)but-3-yn-2-ol.- 10.8.4.9 4,4?-(Thiophene-2,5-diyl)di-(2-methylbut-3-yn-2-ol).- 10.8.4.10 1-Methyl-2(trimethylsilylethynyl)pyrrole.- 10.8.4.11 4-(4-Dimethylaminophenyl)-2-methylbut-3-yn-2-ol.- 10.8.5 Pd/Cu-Catalyzed Couplings of Acetylenic Compounds Using Diisopropylamine as a Solvent.- 10.8.5.1 1,3-Bis(trimethylsilylethynyl)benzene.- 10.8.5.2 3-(Cyclooct-1-enyl)prop-2-yn-1-ol.- 10.8.5.3 1-Trifluoromethyl-2-(trimethylsilylethynyl)benzene.- 10.8.5.4 3-(4-Fluorophenyl)-N,N-dimethylprop-2-yn-1-amine.- 10.8.5.5 1-{3-(1-Ethoxyethoxy)prop-1-ynyl}-4-fluorobenzene.- 10.8.5.6 1-Methoxy-4-(trimethylsilylethynyl)benzene.- 10.8.5.7 4-(3-Furyl)-2-methylbut-3-yn-2-ol.- 10.8.6 Pd/Cu-Catalyzed Couplings with Acetylenic Compounds, Using Piperidine as a Solvent.- 10.8.6.1 1-Ethynylcyclooctene.- 10.8.6.2 2-Chloro-1-ethynylbenzene.- 10.8.6.3 4-Fluoro-1-(trimethylsilylethynyl)benzene.- 10.8.6.4 3-(Trimethylsilylethynyl) thiophene.- 10.8.6.5 1-Methoxy-4-(trimethylsilylethynyl)benzene.- 10.8.6.6 4-N,N-Dimethylamino-1-ethynylbenzene.- 10.8.6.7 5-(Trimethylsilylethynyl)-2,3-dihydro-4H-pyran.- 10.8.7 Preparation of 2-Ethynylarenes and -hetarenes by Pd/Cu-Catalyzed Cross Coupling of Bromoarenes or -hetarenes with 2-Methyl-3-butyn-2-ol and Subsequent KOH-Catalyzed Elimination of Acetone.- 10.8.7.1 4-(2-Thienyl)-2-methylbut-3-yn-2-ol and 2-Ethynylthiophene.- 10.8.7.2 4-(4-Fluorophenyl)-2-methylbut-3-yn-2-ol and 1-Ethynyl-4-fluorobenzene.- 10.8.7.3 4-(4-Chlorophenyl)-2-methylbut-3-yn-2-ol and 4-Chloro-1-ethynylbenzene.- 10.8.7.4 4-(2-Furyl)-2-methylbut-3-yn-2-ol and 2-Ethynylfuran.- 10.8.8 Pd/Cu-Catalyzed Mono-Substitutions with Aryl or Hetaryl Dibromides.- 10.8.8.1 4-(3-Bromothienyl)-2-methylbut-3-yn-2-ol.- 10.8.8.2 3-Bromo-2-(trimethylsilylethynyl)furan.- 10.8.8.3 3-Bromo-2-(trimethylsilylethynyl)thiophene.- 10.8.8.4 4-(2-Bromophenyl)-2-methylbut-3-yn-2-ol.- 10.8.9 Preparation of Disubstituted Acetylenes by Pd/Cu-Catalyzed Reactions with Aryl and Hetaryl Iodides in the Presence of an Amine and Sodium Methoxide.- 10.8.9.1 4-(4-Bromophenyl)-2-methylbut-3-yn-2-ol.- 10.8.9.2 1-(4-Methoxyphenyl)-2-phenylethyne.- 10.8.9.3 3-(Phenylethynyl)thiophene.- 11 Nickel- and Palladium-Catalyzed Cross-Coupling Reactions with Organometallic Intermediates.- 11.1 Introduction.- 11.2 Possibilities of Connecting Organic Groups by Transition Metal Catalysis.- 11.3 Catalysts and Ligands.- 11.4 Leaving Groups.- 11.5 Couplings with Organolithium Compounds.- 11.6 Couplings with Organomagnesium and Organozinc Halides.- 11.7 Cross Couplings with Organoaluminum, Organoboron and Organotin Compounds.- 11.8 Regiochemical and Stereochemical Aspects.- 11.9 Mechanism and Side Reactions.- 11.10 Practical Aspects of Transition-Metal-Catalyzed Couplings.- 11.11 Experimental Section.- 11.11.1 Nickel-Catalyzed Cross-Couplings with Alkylmagnesium Halides.- 11.11.1.1 3-n-Octylthiophene.- 11.11.1.2 3-Cyclohexylthiophene.- 11.11.1.3 3-Benzylthiophene.- 11.11.1.4 (2,2-Dichlorovinyl)cyclohexane.- 11.11.1.5 2-Cyclohexylbenzothiazole.- 11.11.2 Nickel-Catalyzed Cross Couplings with Aryl- and Hetarylmagnesium Halides.- 11.11.2.1 3-Phenylthiophene.- 11.11.2.2 2-(2-Thienyl)furan.- 11.11.2.3 2,2?-Bithienyl.- 11.11.2.4 2-Phenylthiophene.- 11.11.2.5 2,3?-Bithienyl.- 11.11.2.6 2-(4-Fluorophenyl)thiophene.- 11.11.2.7 3-(4-Fluorophenyl)thiophene.- 11.11.2.8 2-Phenylfuran.- 11.11.2.9 1-Phenylcyclooctene.- 11.11.2.10 1-(4-Fluorophenyl)cyclooctene.- 11.11.2.11 4-Methoxybiphenyl.- 11.11.2.12 1-(2-Ethoxyvinyl)-4-fluorobenzene.- 11.11.2.13 2-(2-Ethoxyvinyl)thiophene.- 11.11.2.14 2-(2-Thienyl)pyridine.- 11.11.2.15 3-(2-Thienyl)pyridine.- 11.11.2.16 2,2?:5?2?-Terthiophene.- 11.11.2.17 2,3?:2?2?-Terthiophene.- 11.11.2.18 2,3?:4?,2?-Terthiophene.- 11.11.2.19 2-(2-Fluorophenyl)thiophene.- 11.11.2.20 2-(2-Trifluoromethylphenyl)thiophene.- 11.11.2.21 Unsatisfactory Results.- 11.11.2.22 2-(3-Thienyl)furan.- 11.11.2.23 2-(3-Thienyl)pyridine.- 11.11.2.24 2-Vinylthiophene.- 11.11.2.25 Z-5-(2-Thienyl)pent-4-en-1-ol.- 11.11.3 Palladium-Catalyzed Cross-Couplings with Grignard Compounds and Organozinc Halides.- 11.11.3.1 2-Vinylfuran.- 11.11.3.2 1-Methyl-2-vinylpyrrole.- 11.11.3.3 4-Fluorostyrene.- 11.11.3.4 2-(2-Furyl)pyridine.- 11.11.3.5 3-(2-Furyl)pyridine.- 11.11.3.6 3-Phenylpyridine.- 11.11.3.7 4,4?-Difluorobiphenyl.- 11.11.3.8 2,4?-Difluorobiphenyl.- 11.11.3.9 4-Fluorobiphenyl.- 11.11.3.10 2(3-Fluorophenyl)furan.- 11.11.3.11 2-(1-Methyl-2-pyrrolyl)pyridine.- 11.11.3.12 1-Methyl-2-(2-thienyl)pyrrole.- 11.11.3.13 2-(4-Fluorophenyl)-1-methylpyrrole.- 11.11.3.14 2-(2-Furyl)-1-methylpyrrole.- 11.11.3.15 2,2?:5?,2?-Terfuran.- 11.11.3.16 Thiophene-2,5-diyl-2,2?-difuran.- 11.11.3.17 Thiophene-2,5-diyl-2,2?-difuran.- 11.11.3.18 3-Bromo-2-(2-thienyl)thiophene (Selective Substitution of the 2-Bromine Atom in 2,3-Di-bromothiophene).- 11.11.3.19 2-Bromo-5-(2-thienyl)thiophene.- 11.11.4 Palladium-Catalyzed Reaction of Arylmagnesium Bromides with Trichloroethene.- 11.11.4.1 1,2-Dichlorovinylbenzene.- 11.11.4.2 2-(1,2-Dichlorovinyl)thiophene.- 11.11.4.3 2-(1,2-Dichlorovinyl)furan.- 11.11.4.4 1-(1,2-Dichlorovinyl)-4-fluorobenzene.- 11.11.5 Palladium-Catalyzed Couplings with Alkynylzinc Halides.- 11.11.5.1 2-(1,3-Pentadiynyl)thiophene.- 11.11.5.2 2-(1-Butynyl)thiophene.- 11.11.5.3 Dec-1-en-4-yn-3-one.- 11.11.5.4 1-Phenylbut-2-yn-1-one.- 11.11.6 Palladium-Catalyzed Reaction of Aryl- and Hetarylzinc Halides with Ethyl Chloroformate.- 11.11.6.1 Ethyl-1-methylpyrrole-2-carboxylate (1-Methyl-pyrrole-2-carboxylic Acid Ethyl Ester).- 11.11.7 Palladium-Catalyzed-Cross Couplings with Boronic Acids.- 11.11.7.1 3-(2-Thienyl)pyridine.- 11.11.7.2 2-(3-Nitrophenyl)thiophene.- 11.11.7.3 3-(2-Thienyl)benzaldehyde.- 11.11.7.4 Other Cross Couplings with Boronic Acids.- 11.11.8 Palladium-Catalyzed Cross-Couplings with Tin Derivatives.- 11.11.8.1 3-(4-Methylthiazol-2-yl)pyridine.- 11.11.8.2 2-(4-Methylthiazol-2-yl)thiophene.- 11.11.8.3 3-(2-Furyl)benzaldehyde.- 11.11.8.4 Other Coupling Reactions with Organotin Derivatives.- Tables 9-20.- Index of Reaction Types.- Index of Experimental Procedures.- Complementary Subject Index.