Diamine Ligands in Copper-Catalyzed Reactions

Abstract

The utility of copper-mediated cross-coupling reactions has been significantly increased by the development of mild reaction conditions and the ability to employ catalytic amounts of copper. The use of diamine-based ligands has been important in these advances and in this review we discuss these systems, including the choice of reaction conditions and applications in the synthesis of pharmaceuticals, natural products and designed materials.

Fig. 1

Commercially available diamine ligands

Fig. 2

Critical features of diamine-based ligands.

Scheme 1

Development of Cu-catalyzed amidation of aryl halides by Buchwald.

Scheme 2

Substrate scope of intermolecular Cu-catalyzed amidation.

Scheme 3

Synthesis of enamides from vinyl halides.

Scheme 4

Synthesis of ynamides according to Hsung.

Scheme 5

Synthesis of ynamides according to Evano.

Scheme 6

Synthesis of allenamides according to Trost.

Scheme 7

Arylation of heteroarylamines according to Liu.

Scheme 8

Cu-Catalyzed arylation of NH heterocycles.

Scheme 9

Synthesis of β-azaheterocyclic acid derivatives.

Scheme 10

Synthesis of aryl nitro compounds according to Saito.

Scheme 11

Synthesis of aryl azides by coupling of aryl halides and inorganic azide.

Scheme 12

Cu-catalyzed coupling of secondary phosphites and aryl halides.

Scheme 13

Selective, intramolecular arylation of enolates studied by Li.

Scheme 14

Merck Frosst synthesis of aryl sulfones.

Scheme 15

Synthesis of benzonitriles according to Buchwald.

Scheme 16

Synthesis of indolines according to Buchwald.

Scheme 17

Synthesis of pyrroloindoles according to Evano.

Scheme 18

Li’s investigation of intramolecular amidation of vinyl halides.

Scheme 19

Synthesis of medium-ring nitrogen heterocycles by tandem cross-coupling/ring expansion.

Scheme 20

Albany Molecular Research synthesis of indazoles.

Scheme 21

Synthesis of indolines according to Buchwald.

Scheme 22

Synthesis of quinolones according to Buchwald.

Scheme 23

Synthesis of pyrroles according to Li and Buchwald.

Scheme 24

Synthesis of indoles according to Willis.

Scheme 25

Synthesis of oxazoles according to Buchwald.

Scheme 26

Johnson & Johnson synthesis of benzimidazoles.

Scheme 27

Synthesis of pyrrazoles according to Buchwald.

Scheme 28

Synthesis of imidazoindolones according to Lautens.

Scheme 29

Synthesis of benzimidazoles according to Buchwald.

Scheme 30

Cu-catalyzed halide exchange.

Scheme 31

Vicente’s approach to thioether phenylene aryl iodide monomers

Scheme 32

Applications of the aromatic Finkelstein reaction.

Scheme 33

Whitehead’s synthesis of fluoroshikimic acid.

Scheme 34

Synthesis of photoactivatable cholesterol surrogates according to Spencer.

Scheme 35

Synthesis of an iodinated reboxetine analogue according to Sutherland.

Scheme 36

Sutherland’s synthesis of a peripheral benzodiazepine receptor ligand.

Scheme 37

Koert’s synthesis of factor Xa inhibitors.

Scheme 38

Eli Lilly synthesis of norepinephrine reuptake inhibitors.

Scheme 39

Abbott synthesis of dipeptidyl peptidase IV inhibitors.

Scheme 40

Beghyn’s study of tadalafil analogues.

Scheme 41

Synthesis of non-nucleoside reverse transcriptase inhibitors performed at the Genomics Institute of the Novartis Research Foundation.

Scheme 42

GlaxoSmithKline synthesis of histamine H₃ receptor antagonists.

Scheme 43

Bristols-Myers Squibb synthesis of enamides with aminopeptidase activity.

Scheme 44

Pfizer synthesis of CJ-15,161, a κ-opioid receptor agonist.

Scheme 45

Wyeth synthesis of histamine H₃ receptor antagonists.

Scheme 46

Pfizer synthesis of CRF₁ receptor antagonists.

Scheme 47

Amgen synthesis of inhibitors of receptor tyrosine kinase c-Kit.

Scheme 48

Steinmetzer’s synthesis of a matriptase inhibitor.

Scheme 49

Neurocrine synthesis of melanin-concentrating hormone receptor 1 antagonists.

Scheme 50

Merck synthesis of dipeptidyl peptidase IV inhibitors.

Scheme 51

Schering-Plough synthesis of melanin-concentrating hormone receptor-1 antagonists.

Scheme 52

Athersys synthesis of ramatroban analogues.

Scheme 53

IRBM - Merck Research Laboratories synthesis of inhibitors of the hedgehog signaling pathway.

Scheme 54

Merck synthesis of agonists of G-protein-coupled niacin receptor 109A.

Scheme 55

Applications of Cu/diamine-catalyzed cross-coupling in materials science.

Scheme 56

Synthesis of energy transfer systems by Burgess.

Scheme 57

Nishikawa and Isobe’s synthesis of chartelline alkaloids.

Scheme 58

Evano’s synthesis of paliurine F.

Scheme 59

Applications of Cu/diamine-catalyzed cross-coupling in natural products synthesis.

Scheme 60

Movassaghi’s synthesis of galbulimima alkaloid 13.

Scheme 61

Charette’s synthesis of barrenazine alkaloids.

Scheme 62

Stanovnik’s synthesis of tryprostatin B.

Scheme 63

Andersen’s synthesis of ceratamine alkaloids.

Scheme 64

Kobayashi’s synthesis of hasubanan alkaloids.

Scheme 65

Evano’s synthesis of chaetominine.

Scheme 66

Nakada’s formal synthesis of physostigmine.

Scheme 67

Bergman’s synthesis of vasicoline.