Application of Transition Metal Catalysts in Organic Synthesis

348 Pages·1999·6.188 MB·English

by  Prof. L. Brandsma, Prof. H. D. Verkruijsse, Prof. S. F. Vasilevsky (auth.)

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Application of Transition Metal Catalysts in Organic Synthesis
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L. Brandsma, S. F. Vasilevsky, H. D. Verkruijsse
Application of Transition Metal
Catalysts in Organic Synthesis
, Springer
Prof. L. Brandsma Prof. S. F. Vasilevsky
Prof. H. D. Verkruijsse Russian Academy of Science
Dept. of Preparative Organic Chemistry 630 090 Novosibirsk
Debye Institute Russia
Utrecht University
Padualaan 8
3584 CH Utrecht
The Netherlands
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Preface
The present book may be considered as a continuation of our laboratory manuals
dealing with the chemistry of acetylenes, allenes and polar organometallics. It con
tains a number of experimental procedures for the catalytic use of copper, nickel and
palladium compounds in organic synthesis based on methods described in literature
and carried out by the authors of this book and their coworkers. The original plan
was to cover a much broader field of transition metal chemistry, but this was soon
dropped as being too ambitious. It would take too much time and effort to become
familiar with all experimental methods in the extensive field of transition metal-cat
alyzed organic synthesis, a necessary condition to develop reliable procedures. We
therefore decided to restrict ourselves to sub-fields in which some experience had
been acquired in our laboratory. The various methods are exemplified with proce
dures on a preparative scale, usually 50 or 100 mmolar, using normal laboratory
glassware and reagents and starting compounds which are either relatively cheap or
readily preparable. In addition, literature surveys of the various subjects are given.
We are indebted to Diosynth, DSM and Shell for additional financial and material
support.
Utrecht, November 1997 Lambert Brandsma
Table of Contents
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 ....................... _~ . . . . . . . . . . . . . . . . . . . 2
1.1.2.1 Nickel(II)bromide·bis( triphenylphosphane) ........... 2
1.1.2.2 Nickel(II)chloride·bis(triphenylphosphane) ........... 2
1.1.2.3 Nickel(II)chloride·l,3-bis( diphenylphosphino)
propane........................................... 2
1.1.2.4 Nickel(II)chloride·l,2-bis( diphenylphosphino )ethane ... 2
1.1.2.5 Nickel(II)chloride·l,4-bis( diphenylphosphino )butane . . . 2
1.1.2.6 Nickel(II)chloride·l,1 '-bis( diphenylphosphino)
ferrocene ......................................... 3
1.1.2.7 Nickel(II)bromide·l,l' -bis( diphenylphosphino)
ferrocene ......................................... 3
1.1.2.8 trans-Chloro( 1-naphthyl) bis( triphenylphosphane)
nickel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2.9 trans-Bromo( I-naphthyl)bis( triphenylphosphane)
nickel and trans-Bromo(phenyl)bis
(triphenyl-phosphane)nickel ........................ 4
1.1.3 Palladium Catalysts .................................... , . . . 4
1.1.3.1 Palladiurn(II)chloride·bis(acetonitrile)................ 4
1.1.3.2 Palladium(II)chloride·bis(benzonitrile)............... 4
1.1.3.3 Palladiurn(II)chloride·bis( triphenylphosphane) ........ 4
1.1.3.4 Palladium(II)chloride·l,4-bis( diphenylphosphino)
butane ...........' ................................. 4
1.1.3.5 Palladium(II)chloride·l,l' -bis( diphenylphosphino)
ferrocene ......................................... 5
1.1.3.6 Tetrakis(triphenylphosphane)palladium(O)............ 5
1.1.3.7 Tris(dibenzylideneacetone)dipalladium(O)·chloroform.. 6
1.2 Ligands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.1 l,n-Bis(diphenylphosphino)alkanes (n= 2,3,4) . . . . . . . . . . . . . . . . . 6
1.2.1.1 1,2-Bis( diphenylphosphino )ethane ................... 7
1.2.1.2 1,3-Bis(diphenylphosphino)propane.................. 7
1.2.1.3 1,4-Bis( diphenylphosphino )butane ................... 8
VIII Table of Contents
1.2.2 1,l'-Bis(diphenylphosphino)ferrocene. ... ... ... . .. .. ... ... ... 8
1.2.3 Triarylphosphanes and Tri(hetaryl)phosphanes . . . . . . . . . . . . . . . . 9
1.3 Organometallic Reagents .......................................... 10
1.3.1 Preparation of Grignard Reagents from Mg and
Organic Halides ........................................... 10
1.3.2 Preparation of Organomagnesium and Organozinc Halides
by Lithium-Magnesium or Lithium-Zinc Exchange ............ 12
1.3.3 Preparation of Organoaluminum Intermediates. . . . . . . . . . . . . . .. 13
1.3.4 Preparation of Organoboron and Organotin Intermediates .. . . . . 13
1.3.4.1 2-Thiopheneboronic Acid ........................... 13
1.3.4.2 2-Furanboronic Acid ............................... 14
1.3.4.3 4-(Fluorophenyl)boronic Acid ....................... 14
1.3.4.4 (2-Methoxyphenyl)boronic Acid ..................... 15
1.3.4.5 2-Tributylstannylfuran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.4.6 1-Methyl-2-tributylstannylpyrrole.................... 15
1.3.4.7 4-Methyl-2-tributylstannylthiazole ................... 16
1.3.4.8 Stannylation of Ethyl Vinyl Ether..... ...... . ......... 17
2 Procedures for the Preparation of Halogen Compounds . . . . . . . . . . . . . . . . . . . 19
2.1 sp-Halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1.1 1-Bromo-1-propyne and 1-Bromo-1-butyne .. ...... . ... . ... ... 19
2.1.2 1-Bromo-1-pentyne and 1-Bromo-1-hexyne .. ... . .. . ... . . .. ... 20
2.1.3 Other 1-Bromo-1-alkynes ... . .... ...... .. ... ....... .. ... .. .. 21
2.1.4 Reaction of Alkynyllithium with Iodine in Organic Solvents. . . .. 22
2.1.5 Preparation ofIodoacetylenes from Lithiated Acetylenes
and Iodine in Liquid Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 22
2.2 Aryl and Hetaryl Halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
2.2.1 2-Bromothiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
2.2.2 2,5-Dibromothiophene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 25
2.2.3 2,3,5-Tribromothiophene ................................... 25
2.2.4 3-Bromothiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 26
2.2.5 2,3-Dibromothiophene. . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 26
2.2.6 3,4-Dibromothiophene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 27
2.2.7 2,4-Dibromothiophene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
2.2.8 2-Bromofuran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 29
2.2.9 2,3-Dibromofuran. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 30
2.2.10 3-Bromofuran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31
2.2.11 2,5-Dibromofuran ......................................... 31
2.2.12 2-Iodothiophene........................................... 32
2.2.13 3-Iodothiophene........................................... 33
2.2.14 2-Iodofuran............................................... 33
2.2.15 2-Iodo-1-methylimidazole .................................. 34
Table of Contents IX
2.2.16 2-Iodo-l-methylpyrrole .................................... 34
2.2.17 I-Bromo-4-iodobenzene.................................... 35
2.2.18 3-Bromoquinoline......................................... 36
2.3 Olefinic, Cycloolefinic and Allenic Halides ........................... 36
2.3.1 I-Bromo-2-methylpropene ..... . .... . .... .. ....... ... .... ... 36
2.3.2 a-Bromostyrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 37
2.3.3 2-Bromo-l-ethoxyethene ................................... 38
2.3.4 3-Bromo-5,6-dihydro-4H-pyran ............................. 38
2.3.5 I-Bromocyclooctene ....................................... 39
2.3.6 l-Chlorocyclohexene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 40
2.3.7 Z-I,4-Dibromo-2-butene and I-Bromo-l,3-butadiene . . .... .... 40
2.3.8 E-l,4-Dibromo-2-butene and I-Bromo-l,3-butadiene .......... 42
2.3.9 2-Bromo-l,3-butadiene ....... ........ ... ... ... ... . . ... ... .. 42
2.3.10 I-Bromo-3-methyl-1,2-butadiene ........•................... 43
2.3.11 I-Bromo-1,2-butadiene ..... ....... . . . ..... ........... ...... 44
2.3.12 1-Bromocyclohexene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 44
2.3.13 1-Bromocyclopentene ...................................... 45
2.3.14 E-l-Bromo-1-octene ....................................... 46
2.3.15 E-1-Iodo-1-heptene ... ..... ... . . .. . .... . .. ... ... . ... . . .. ... 47
3 Cross-Coupling Between l-Alkynes and I-Bromoalkynes .................. 49
3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 49
Table 1 ................................................................ 50
3.2 Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 53
3.3 Relative Reactivities of the Acetylene and the Bromoacetylene .......... 53
Table 2 ................................................................ 54
3.4 Conditions for the Coupling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 56
3.5 Choice of the Reaction Partners. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
3.6 Side Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
3.7 Experimental Part. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 58
3.7.1 General Remarks and Some Observations. . . . . . . . . . . . . . . . . . . .. 58
3.7.2 Performance of Cu-Catalyzed Cadiot-Chodkiewicz Couplings ... 59
3.7.3 Typical Procedure for the Pd/Cu-Catalyzed Cross Coupling
Between 1-Bromo-1-alkynes and Acetylenes .................. 60
x Table of Contents
4 Copper-Catalyzed Aminoalkylation of Acetylenes ........................ 61
4.1 Introduction, Scope and Mechanism ................................ 61
4.2 Experimental Part ................................................ 63
4.2.1 Reaction of Acetylenic Alcohols with Dimethylaminomethanol .. 63
4.2.2 General Procedure for the Mannich Reaction of Acetylenes
Without an OH-Function ................................... 64
4.2.3 Mannich Reactions with Gaseous Acetylenes .................. 66
5 Copper(I)-Halide-Catalyzed Oxidative Coupling of Acetylenes ............. 67
5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 67
5.2 Methods, Scope and Limitations .................................... 67
5.3 About the Mechanism ............................................. 69
5.4 Experimental Part ................................................ 71
5.4.1 Oxidative Coupling of Prop argyl Alcohol Catalyzed by
Copper(I)Chloride in Aqueous Medium ...................... 71
5.4.2 Oxidative Couplings Catalyzed by Copper(I)Chloride·TMEDA
in Acetone ................................................ 72
5.4.2.1 Oxidative Coupling of Methyl Propargyl Ether ......... 72
5.4.2.2 Oxidative Coupling of 3-Butyn-2-o1 . . . . . . . . . . . . . . . . . .. 73
5.4.2.3 Oxidative Coupling of2-Methyl-3-butyn-2-o1 .......... 73
5.4.2.4 Oxidative Coupling of 3-Butyn-1-o1 . . . . . . . . . . . . . . . . . .. 74
5.4.2.5 Oxidative Coupling of 1-Methoxy-1-buten-3-yne ....... 74
5.4.2.6 Oxidative Coupling of Arylacetylenes ................. 75
5.4.2.7 Oxidative Coupling of Prop argyl Alcohol... .. .... .. ... 75
5.4.3 Oxidative Couplings Catalyzed by Copper(I)Chloride·TMEDA
in N,N-Dimethylformamide ...... ...... ..... ........ . . .. .... 76
5.4.3.1 Oxidative Coupling of 1,1-Diethoxy-2-propyne . . ... .... 76
5.4.3.2 Oxidative Coupling of Ethyl Prop argyl Sulfide. . . . . . . . .. 76
5.4.4 Oxidative Couplings Catalyzed by Copper(I)Chloride
in Pyridine ............................................... 77
5.4.4.1 Oxidative Coupling of 4-Butyn-1-o1 ........ . ... . ... ... 77
5.4.4.2 Oxidative Coupling of2-Ethynylpyridine ... . .... ... ... 78
5.4.5 Oxidative Couplings Catalyzed by Copper(I)Chloride and
Diazabicydoundecene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 78
5.4.5.1 Oxidative Coupling of 1-Butyne ... . . . . . . . . . . . . . . . . . .. 78
5.4.5.2 Oxidative Coupling of2-Ethynyl-1-methylpyrrole ...... 79
5.4.5.3 Oxidative Coupling of t -Butylacetylene . . . . . . . . . . . . . . .. 79
5.4.6 Oxidative Coupling of Trimethylsilylacetylene ................. 80
5.4.7 Oxidative Coupling of the HCI-Salt of
3-Amino-3-methyl-1-butyne ................................ 80
Table of Contents XI
5.5 Summary of Experimental Conditions for Oxidative Couplings ......... 81
Table 3 ................................................................ 82
6 Copper(I)-Halide-Catalyzed Substitution of sp2-Halogen by Alkoxide . . . . . .. 85
6.1 Introduction ....................................................... 85
6.2 Scope and Limitations of the Copper-Catalyzed Nucleophilic
Substitution of Sp2_ Halogen by Alkoxy Groups . . . . . . . . . . . . . . . . . . . . . . .. 86
Table 4 ................................................................ 87
6.3 Mechanistic Investigations ......................................... 93
6.4 Reaction Conditions .............................................. 93
6.4.1 Solvent and Reaction Temperature ........................... 93
6.4.2 The Catalyst .............................................. 94
6.5 Differences in the Reactivities of the Various sp2_ Halides . . . . . . . . . . . . . .. 95
6.6 Side Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 96
6.7 Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 97
6.8 Experimental Part ................................................ 97
6.8.1 General. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 97
6.8.1.1 Reaction Conditions and Observations. . . . . . . . . . . . . . .. 97
6.8.1.2 Apparatus and Equipment. . . . . . . . . . . . . . . . . . . . . . . . . .. 98
6.8.2 Methoxylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 99
6.8.2.1 2-Methoxythiophene ............................... 99
6.8.2.2 3-Methoxythiophene ............................... 100
6.8.2.3 3-Methoxypyridine ................................. 100
6.8.2.4 3,4-Dimethoxythiophene ............................ 101
6.8.2.5 I-Methoxycyclooctene .............................. 101
6.8.3 Other Alkoxylations ........................................ 102
6.8.3.1 2-Ethoxythiophene ................................. 102
6.8.3.2 3-Ethoxythiophene ................................. 102
6.8.3.3 3-Isopropoxythiophene ............................. 102
6.8.3.4 2-(2'Dimethylaminoethoxy)furan .................... 102
6.8.3.5 2-(2'Dimethylaminoethoxy)thiophene ................ 103
6.8.3.6 1-(2'Dimethylaminoethoxy)cyclooctene............... 103
6.8.3.7 2-(2'Methoxyethoxy)thiophene ....................... 103
6.8.3.8 1,4-Bis(2,2,2-trifluoroethoxy)benzene ................. 104