Application of Transition Metal Catalysts in Organic Synthesis,9783540655503

Application of Transition Metal Catalysts in Organic Synthesis

by ; ;
ISBN13: 9783540655503
ISBN10: 3540655506
Format: Paperback
Pub. Date: 1999-04-01
Publisher(s): Springer Verlag
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Summary

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.

Table of Contents

Catalysts, Ligands and Reagents
1(18)
Catalysts
1(5)
Copper Halides
1(1)
Solubilization of Copper(I) Halides
1(1)
Nickel Catalysts
2(1)
Nickel(II)bromide bis(tripheylphospahe)
2(1)
Nickel(II)chloride bis(triphenylphospahe)
2(1)
Nickel(II)chloride 1,3-bis(diphenylphosphino) propane
2(1)
Nickel(II)chloride 1,2-bis(diphenylphosphino)ethane
2(1)
Nickel(II)chloride 1,4-bis(diphenylphosphino)butane
2(1)
Nickel(II)chloride 1,1'-bis(diphenylphosphino) ferrocene
3(1)
Nickel(II)bromide 1,1'-bis(diphenylphosphino) ferrocene
3(1)
trans-Chloro(1-naphthyl)bis(tripheylphosphane) nickel
3(1)
trans-Bromo(1-naphthyl)bis(tripheylphosphane) nickel and trans-Bromo(phenyl)bis (triphenyl-phosphane)nickel
4(1)
Palladium Catalysts
4(1)
Palladium(II)chloride bis(acetonitrile)
4(1)
Palladium(II)chloride bis(benzonitrile)
4(1)
Palladium(II)chloride bis(triphenylphosphane)
4(1)
Palladium(II)chloride 1,4-bis(diphenylphosphino) butane
4(1)
Palladium(II)chloride 1,1'-bis(diphenylphosphino) ferrocene
5(1)
Tetrakis(triphenylphosphane)palladium(0)
5(1)
Tris(dibenzylideneacetone)dipalladium(0) chloroform
6(1)
Ligands
6(4)
1,n-Bis(diphenylphosphino)alkanes (n= 2,3,4)
6(1)
1,2-Bis(diphenylphosphino)ethane
7(1)
1,3-Bis(diphenylphosphino)propane
7(1)
1,4-Bis(diphenylphosphino)butane
8(1)
1,1'-Bis(diphenylphosphino)ferrocene
8(1)
Triarylphosphanes and Tri(hetaryl)phosphanes
9(1)
Organometallic Reagents
10(9)
Preparation of Grignard Reagents from Mg and Organic Halides
10(2)
Preparation of Organomagnesium and Organozinc Halides by Lithium--Magnesium or Lithium-Zinc Exchange
12(1)
Preparation of Organoaluminium Intermediates
13(1)
Preparation of Organoboron and Organotin Intermediates
13(1)
2-Thiopheneboronic Acid
13(1)
2-Furanboronic Acid
14(1)
4-(Fluorophenyl)boronic Acid
14(1)
(2-Methoxyphenyl)boronic Acid
15(1)
2-Tributylstannylfuran
15(1)
1-Methyl-2-tributylstannylpyrrole
15(1)
4-Methyl-2-tributylstannylthiazole
16(1)
Stannylation of Ethyl Vinyl Ether
17(2)
Procedures for the Preparation of Halogen Compounds
19(30)
sp-Halides
19(5)
1-Bromo-1-propyne and 1-Bromo-1-butyne
19(1)
1-Bromo-1-pentyne and 1-Bromo-1-hexyne
20(1)
Other 1-Bromo-1-alkynes
21(1)
Reaction of Alkynyllithium with Iodine in Organic Solvents
22(1)
Preparation of Iodoacetylenes from Lithiated Acetylenes and Iodine in Liquid Ammonia
22(2)
Aryl and Hetaryl Halides
24(12)
2-Bromothiophene
24(1)
2,5-Dibromothiophene
25(1)
2,3,5-Tribromothiophene
25(1)
3-Bromothiophene
26(1)
2,3-Dibromothiophene
26(1)
3,4-Dibromothiophene
27(1)
2,4-Dirbomothiophene
28(1)
2-Bromofuran
29(1)
2,3-Dibromofuran
30(1)
3-Bromofuran
31(1)
2,5-Dibromofuran
31(1)
2-Iodothiophene
32(1)
3-Iodothiophene
33(1)
2-Iodofuran
33(1)
2-Iodo-1-methylimidazole
34(1)
2-Iodo-1-methylpyrrole
34(1)
1-Bromo-4-iodobenzene
35(1)
3-Bromoquinoline
36(1)
Olefinic, Cycloolefinic and Allenic Halides
36(13)
1-Bromo-2-methylpropene
36(1)
α-Bromostyrene
37(1)
2-Bromo-1-ethoxyethene
38(1)
3-Bromo-5,6-dihydro-4H-pyran
38(1)
1-Bromocyclooctene
39(1)
1-Chlorocyclohexene
40(1)
Z-1,4-Dibromo-2-butene and 1-Bromo-1,3-butadiene
40(2)
E-1,4-Dibromo-2-butene and 1-Bromo-1,3-butadiene
42(1)
2-Bromo-1,3-butadiene
42(1)
1-Bromo-3-methyl-1,2-butadiene
43(1)
1-Bromo-1,2-butadiene
44(1)
1-Bromocyclohexene
44(1)
1-Bromocyclopentene
45(1)
E-1-Bromo-1-octene
46(1)
E-1-Iodo-1-heptene
47(2)
Cross-Coupling Between 1-Alkynes and 1-Bromoalkynes
49(12)
Introduction
49(4)
Table 1
50(3)
Scope and Limitations
53(1)
Relative Reactivities of the Acetylene and the Bromoacetylene
53(3)
Table 2
54(2)
Conditions for the Coupling
56(1)
Choice of the Reaction Partners
57(1)
Side Reactions
57(1)
Experimental Part
58(3)
General Remarks and Some Observations
58(1)
Performance of Cu-Catalyzed Cadiot-Chodkiewicz Couplings
59(1)
Typical Procedure for the Pd/Cu-Catalyzed Cross Coupling Between 1-Bromo-1-alkynes and Acetylenes
60(1)
Copper-Catalyzed Aminoalkylation of Acetylenes
61(6)
Introduction, Scope and Mechanism
61(2)
Experimental Part
63(4)
Reaction of Acetylenic Alcohols with Dimethylaminomethanol
63(1)
General Procedure for the Mannich Reaction of Acetylenes Without an OH-Function
64(2)
Mannich Reactions with Gaseous Acetylenes
66(1)
Copper(I)-Halide-Catalyzed Oxidative Coupling of Acetylenes
67(18)
Introduction
67(1)
Methods, Scope and Limitations
67(2)
About the Mechanism
69(2)
Experimental Part
71(10)
Oxidative Coupling of Propargyl Alcohol Catalyzed by Copper(I)Chloride in Aqueous Medium
71(1)
Oxidative Couplings Catalyzed by Copper(I)Chloride TMEDA in Acetone
72(1)
Oxidative Coupling of Methyl Propargyl Ether
72(1)
Oxidative Coupling of 3-Butyn-2-ol
73(1)
Oxidative Coupling of 2-Methyl-3-butyn-2-ol
73(1)
Oxidative Coupling of 3-Butyn-1-ol
74(1)
Oxidative Coupling of 1-Methoxy-1-buten-3-yne
74(1)
Oxidative Coupling of Arylacetylenes
75(1)
Oxidative Coupling of Propargyl Alcohol
75(1)
Oxidative Couplings Catalyzed by Copper(I)Chloride TMEDA in N,N-Dimethylformamide
76(1)
Oxidative Coupling of 1,1-Diethoxy-2-propyne
76(1)
Oxidative Coupling of Ethyl Propargyl Sulfide
76(1)
Oxidative Couplings Catlayzed by Copper(I)Chloride in Pyridine
77(1)
Oxidative Coupling of 4-Butyn-1-ol
77(1)
Oxidative Coupling of 2-Ethynylpridine
78(1)
Oxidative Couplings Catalyzed by Copper(I)Chloride and Diazabicycloundecene
78(1)
Oxidative Coupling of 1-Butyne
78(1)
Oxidative Coupling of 2-Ethynyl-1-methylpyrrole
79(1)
Oxidative Coupling of t-Butylacetylene
79(1)
Oxidative Coupling of Trimethylsilyacetylene
80(1)
Oxidative Coupling of the HCl-Salt of 3-Amino-3-methyl-1-butyne
80(1)
Summary of Experimental Conditions for Oxidative Couplings
81(4)
Table 3
82(3)
Copper(I)-Halide-Catalyzed Substitution of sp2-Halogen by Alkoxide
85(22)
Introduction
85(1)
Scope and Limitations of the Copper-Catalyzed Nucleophilic Substitution of sp2-Halogen by Alkoxy Groups
86(7)
Table 4
87(6)
Mechanistic Investigations
93(1)
Reaction Conditions
93(2)
Solvent and Reaction Temperature
93(1)
The Catalyst
94(1)
Differences in the Reactivities of the Various sp2-Halides
95(1)
Side Reactions
96(1)
Applications
97(1)
Experimental Part
97(10)
General
97(1)
Reaction Conditions and Observations
97(1)
Apparatus and Equipment
98(1)
Methoxylation
99(1)
2-Methoxythiophene
99(1)
3-Methoxythiophene
100(1)
3-Methoxypyridine
100(1)
3,4-Dimethoxythiophene
101(1)
1-Methoxycyclooctene
101(1)
Other Alkoxylations
102(1)
2-Ethoxythiophene
102(1)
3-Ethoxythiophene
102(1)
3-Isopropoxythiophene
102(1)
2-(2'Dimethylaminoethoxy)furan
102(1)
2-(2'Dimethylaminoethoxy)thiophene
103(1)
1-(2'Dimethylaminoethoxy)cyclooctene
103(1)
2-(2'Methyoxyethoxy)thiophene
103(1)
1,4-Bis(2,2,2,-trifluoroethoxy)benzene
104(3)
Copper-Catalyzed Carbon-Carbon Bond Formation by 1,1-and 1,3-Substitution Reactions
107(34)
Introduction
107(1)
Displacement of Halide, Tosylate and Acetate in Saturated Compounds
108(1)
Ring Opening of Saturated Epoxides
109(1)
Reactions with Allylic Substrates
110(4)
Reactions with Propargylic and Allenic Substrates
114(2)
About the Mechanism of Copper Catalyzed Substitutions
116(2)
Experimental Section
118(23)
Alkylation Reactions with Halides and Tosylates
118(1)
2,2,7,7-Tetramethyloctane
118(1)
5,5-Dimethylhexan-1-ol
119(1)
Selective Substitution of Bromine in 1-Bromo-4-chlorobutane
120(1)
Selective Mono-Substitutions with 1,n-Dibromoalkanes
120(1)
Displacement of Tosylate in Alkyl Tosylates
121(1)
Neopentylbenzene
122(1)
Benzyl-Aryl Couplings
122(1)
t-Butylallen
123(1)
Coupling Between Propargyl Alcohol and Propargyl Chloride in Aqueous Solution
124(1)
Couplings Between Acetylenic Gringard Reagents and Allyl Bromide or Propargyl Bromide
124(1)
Reactions of Grignard Reagents with Propargylic Tosylates
125(1)
Substitutions with Cyclic and Non-Cyclic Ethers
126(1)
Preparation of 1-Alkenyl Ethers from Grignard Reagents and 1,1-Diethoxy-2-propene
126(1)
Reaction of Phenylmagnesium Bromide with Cyclohexene Oxide
127(1)
Preparation of Allenic Ethers from Propargylaldehyde Diethylacetal and Grignard Reagents
127(1)
Cyclohexylallene
128(1)
Preparation of Allenic Alcohols from Acetylenic Expoxides and Grignard Reagents
128(1)
Reaction of 2-Ethynyltetrahydropyran with a Grignard Reagent
129(1)
3-Cyclopentyl-1-propyne
129(1)
Table 5
130(6)
Table 6
136(5)
Nickel Catalyzed Iodo-Dechlorination and Iodo-Debromination of sp2-Halides
141(8)
Introduction
141(1)
Scope and Limitations
141(2)
Mechanistic Investigations
143(1)
Side Reactions
143(2)
Experimental Procedures
145(2)
Conversion of 1-Bromocyclooctene into 1-Iodocyclooctene
145(1)
1-Iodocyclohexene from 1-Chlorocyclohexene (Zn/NiBr2)
146(1)
1-Iodocyclohexene from 1-Chlorocyclohexene (Ni(COD)2)
147(1)
Conclusions from our Investigations
147(2)
Nickel- and Palladium-Catalyzed Cyanation of sp2-Halides and sp2-Triflates
149(30)
Introduction
149(1)
Scope and Limitations
149(14)
Table 7
151(12)
Mechanism of the Nickel Catalyzed Cyanation
163(3)
Methods of Performing Nickel Catlayzed Cyanations
166(2)
Relative Reactivities of sp2-Halides
168(1)
Side Reactions
168(1)
Catalysis by Palladium Compounds
169(1)
Experimental Part
170(9)
General Procedure for the Nickel Catalyzed Cyanation of sp2-Halides in Absolute Ethanol
171(3)
General Procedures for Cyanations Proceeding Under the Influence of a NiO-Catalyst Generated by Reducing a NiII-Precatalyst with Zinc Power
174(1)
Cyanation of p-Chlorobenzotrifluoride
175(1)
Cyanation of 1-Bromocyclooctene
176(1)
Palladium-Catalyzed Cyanation of Aryl Iodides
176(1)
Palladium-Catalyzed Cyano-Debromination of Bromoolefins
177(2)
Couplings of Acetylenes with sp2-Halides
179(48)
Introduction
179(1)
Mechanistic Considerations
180(1)
Scope and Limitations
181(10)
Table 8
183(8)
Relative Rates of Coupling
191(1)
Regiochemistry and Stereochemistry
191(2)
Synthetic Applications of the Cross-Coupling Reactions with Acetylenes
193(5)
Simple Applications of the Cross-Coupling
193(1)
Synthesis of Structurally Interesting Acetylenic Compounds
194(1)
Coupling Followed by Cyclization
195(1)
Synthesis of Biologically Interesting Compounds
196(1)
Special Methods
197(1)
Practical Aspects of Coupling Reactions
198(3)
Performance of the Reactions and Isolation of the Products
198(2)
Choice of the Solvent and Catalysts for Coupling Reactions
200(1)
Experimental Section
201(26)
Pd/Cu-Catalyzed Cross Couplings of Acetylenic Compounds with Aliphatic sp2-Halides Using Diethylamine as a Solvent
201(1)
4-Penten-2-yn-1-ol
201(1)
4-Methyl-4-penten-2-yn-1-ol
202(1)
1-Nonen-3-yne
203(1)
2-Methyl-6-trimethylsilylhexa-2,3-dien-5-yne
203(1)
6-Ethoxy-2-methylhex-5-en-3-yn-2-ol
203(1)
6-Ethoxyhex-5-en-3-yn-2-ol
204(1)
2,5-Dimethylhex-5-en-3-yn-2-ol
204(1)
2,6-Dimethlhep-5-en-3-yn-2-ol
204(1)
5-Trimethylsilylethynyl-2,3-dihydro-4H-pyran
204(1)
6-Chloro-2-methylhex-5-en-3-yn-2-ol
205(1)
1-Chlorodec-1-en-3-yne
205(1)
2-Chlorooct-1-en-3-yne
206(1)
Other Cross Couplings, Using Similar Conditions
206(1)
Pd/Cu-Catalyzed Couplings of Acetylene with Aryl and Hetaryl Halides
206(1)
1,2-Bis (4-acetylphenyl)ethyne
206(1)

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