review. We believe that this information is beneficial for the people who are doing
similar studies in this field. Catalyst optimization is of critical importance to catalyst
development, thus the information we have included in this review contains very
valuable information for the newcomers to the field. To our knowledge this is the
first review that covers the title chemistry.
Keywords Aryl halides Á C-N bond formation Á Copper catalyst Á Cross-Coupling Á
Heterocycles Á Heterogeneous Á Reusable catalysts
Contents
1 Heterogeneous or Reusable Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2 Green Chemistry of Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3 Copper-Catalyzed Coupling Reactions in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4 CuI/L-Proline/[Bmim][BF 4 ] Ionic Liquids with Aryl/Heteroaryl Bromides . . . . . . . . . . . . . 122
5 CuI/L-Proline/[Bmim]BF 4 Ionic Liquids with Vinyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6 CuO Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7 Cu 2 O Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
8 Copper-Exchanged Fluorapatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
9 CuI Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
10 Cu(II)-NaY Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
11 Nanocrystalline Copper(II) Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
12 Cu 2 O-Coated Cu Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
13 Resin-Supported Sulfonato-Cu-(salen) Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
14 Silica Immobilized Copper Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
15 Bio-degradable Cellulose-Supported Copper(0) Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
16 Polyaniline-Cu Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
17 Copper–Aluminum Hydrotalcite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
18 C–N Bond Forming Cross-Coupling Reactions Using Arylboronic Acids . . . . . . . . . . . . . . 152
19 Recently Reported Copper Heterogeneous Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
20 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
1 Heterogeneous or Reusable Catalysis
Organic synthesis employing heterogeneous catalysts has several beneficial effects to
the environment. Because it involves the reuse of precious metal catalysts, it forms less
waste and results in lower metal contamination in the final pharmaceutically important
molecules. However, solid-supported catalysts are complex assemblies. Their preparation and characterization are challenging tasks. Minor changes to their preparation
conditions can significantly influence the delicate balance of conflicting demands: high
activity, high selectivity, and a long lifetime [1]. Several varieties of heterogeneous or
reusable catalytic systems are known depending on the type of application.
120
M.L. Kantam et al.
similar studies in this field. Catalyst optimization is of critical importance to catalyst
development, thus the information we have included in this review contains very
valuable information for the newcomers to the field. To our knowledge this is the
first review that covers the title chemistry.
Keywords Aryl halides Á C-N bond formation Á Copper catalyst Á Cross-Coupling Á
Heterocycles Á Heterogeneous Á Reusable catalysts
Contents
1 Heterogeneous or Reusable Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2 Green Chemistry of Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3 Copper-Catalyzed Coupling Reactions in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4 CuI/L-Proline/[Bmim][BF 4 ] Ionic Liquids with Aryl/Heteroaryl Bromides . . . . . . . . . . . . . 122
5 CuI/L-Proline/[Bmim]BF 4 Ionic Liquids with Vinyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6 CuO Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7 Cu 2 O Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
8 Copper-Exchanged Fluorapatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
9 CuI Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
10 Cu(II)-NaY Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
11 Nanocrystalline Copper(II) Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
12 Cu 2 O-Coated Cu Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
13 Resin-Supported Sulfonato-Cu-(salen) Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
14 Silica Immobilized Copper Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
15 Bio-degradable Cellulose-Supported Copper(0) Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
16 Polyaniline-Cu Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
17 Copper–Aluminum Hydrotalcite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
18 C–N Bond Forming Cross-Coupling Reactions Using Arylboronic Acids . . . . . . . . . . . . . . 152
19 Recently Reported Copper Heterogeneous Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
20 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
1 Heterogeneous or Reusable Catalysis
Organic synthesis employing heterogeneous catalysts has several beneficial effects to
the environment. Because it involves the reuse of precious metal catalysts, it forms less
waste and results in lower metal contamination in the final pharmaceutically important
molecules. However, solid-supported catalysts are complex assemblies. Their preparation and characterization are challenging tasks. Minor changes to their preparation
conditions can significantly influence the delicate balance of conflicting demands: high
activity, high selectivity, and a long lifetime [1]. Several varieties of heterogeneous or
reusable catalytic systems are known depending on the type of application.
120
M.L. Kantam et al.