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Review
. 2008;47(34):6338-61.
doi: 10.1002/anie.200800497.

Biaryl phosphane ligands in palladium-catalyzed amination

David S Surry  1 , Stephen L Buchwald
Affiliations
Review

Biaryl phosphane ligands in palladium-catalyzed amination

David S Surry et al. Angew Chem Int Ed Engl. 2008.

Abstract

Palladium-catalyzed amination reactions of aryl halides have undergone rapid development in the last 12 years, largely driven by the implementation of new classes of ligands. Biaryl phosphanes have proven to provide especially active catalysts in this context. This Review discusses the application of these catalysts in C-N cross-coupling reactions in the synthesis of heterocycles and pharmaceuticals, in materials science, and in natural product synthesis.

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Figures

Figure 1
Figure 1
Representative commercially available biaryl phosphine ligands.
Figure 2
Figure 2
Structure of ligand 9.
Figure 3
Figure 3
Palladacycle structure.
Figure 4
Figure 4
Palladium-arene interaction.
Figure 5
Figure 5
Important structural features of dialkylbiaryl phosphines.
Figure 6
Figure 6
Solid-supported and solubilized biaryl dialkylphosphine ligands.
Scheme 1
Scheme 1
Synthesis of biaryl phosphines.
Scheme 2
Scheme 2
Proposed catalytic cycle.
Scheme 3
Scheme 3
Movassaghi's coupling of a vinyl triflate with 3-cyanoindole.
Scheme 4
Scheme 4
Willis’ coupling of amides with vinyl triflates.
Scheme 5
Scheme 5
Barluenga's coupling of vinyl chlorides with amines.
Scheme 6
Scheme 6
Barluenga's coupling of 1-halo-1,3-butadienes with amines.
Scheme 7
Scheme 7
Barluenga's coupling of vinyl bromides with hydrazines.
Scheme 8
Scheme 8
Barluenga's coupling of vinyl bromides with trialkylsilylamines.
Scheme 9
Scheme 9
Barluenga's synthesis of indoles from vinyl bromides and 2-haloanilines.
Scheme 10
Scheme 10
Barluenga's synthesis of indoles from vinyl bromides, 1,2-dihaloarenes and anilines.
Scheme 11
Scheme 11
Willis’ synthesis of indoles from 2-(2-haloalkenyl)-aryl halides and anilines.
Scheme 12
Scheme 12
Lautens’ tandem amination/Suzuki heterocycle synthesis.
Scheme 13
Scheme 13
Cacchi's synthesis of indoles by cyclization of o-alkynyltrifluoroacetanilides in the presence of aryl chlorides.
Scheme 14
Scheme 14
Merck synthesis of indoles from vinylogous amides and 1,2-dihaloarenes.
Scheme 15
Scheme 15
Synthesis of indoles by arylation of benzophenone hydrazones followed by cyclization.
Scheme 16
Scheme 16
Boehringer Ingelheim heterocycle synthesis by arylation of benzophenone hydrazones.
Scheme 17
Scheme 17
Buchwald's synthesis of benzimidazoles from o-haloacetanilides and anilines.
Scheme 18
Scheme 18
Nozaki's synthesis of carbazoles from 2,2’-dihalobiphenyls and amines.
Scheme 19
Scheme 19
Merck synthesis benzoimidazolones by cyclization of ureas.
Scheme 20
Scheme 20
GlaxoSmithKline synthesis of antiherpes agents.
Scheme 21
Scheme 21
Merck synthesis of mGlu5 receptor antagonists.
Scheme 22
Scheme 22
Johnson & Johnson synthesis of PDE5 inhibitors.
Scheme 23
Scheme 23
Merck Frosst synthesis of caspase-3 inhibitors.
Scheme 24
Scheme 24
Vince's synthesis of HIV integrase inhibitors.
Scheme 25
Scheme 25
Kobayashi's synthesis of hybrids of caffeine and eudistomin D.
Scheme 26
Scheme 26
Wentland's synthesis of benzazocine analogues.
Scheme 27
Scheme 27
Begtrup's use of benzophenone imine in the synthesis of 2-fluoronorapomorphine.
Scheme 28
Scheme 28
Novartis synthesis of estrogen receptor modulators.
Scheme 29
Scheme 29
Abbott synthesis of histamine receptor H3 receptor antagonists.
Scheme 30
Scheme 30
Merck synthesis of estrogen receptor ligands.
Scheme 31
Scheme 31
Lautens's synthesis of KDR kinase inhibitors.
Scheme 32
Scheme 32
Bristol-Myers Squibb synthesis of substituted 7-azaindoles.
Scheme 33
Scheme 33
Pfizer synthesis of a κ-opiod receptor agonist.
Scheme 34
Scheme 34
Pfizer synthesis of N-aryloxazolidinones.
Scheme 35
Scheme 35
Burgos’ and Vaquero's synthesis of variolin derivatives.
Scheme 36
Scheme 36
Tanatani's synthesis of a non-steroidal/non-anilide type androgen antagonist.
Scheme 37
Scheme 37
Athersys synthesis of noscapine analogues.
Scheme 38
Scheme 38
Merck synthesis calcium channel ligands
Scheme 39
Scheme 39
GlaxoSmithKline syntheis of CRF1 receptor antagonists.
Scheme 40
Scheme 40
Bristol-Myers Squibb synthesis of phosphodiesterase 7 inhibitors.
Scheme 41
Scheme 41
Wyeth synthesis of Ecopladib.
Scheme 42
Scheme 42
Augustyns’ synthesis of dipeptidyl peptidase II inhibitors.
Scheme 43
Scheme 43
Wüst's synthesis of radiolabelled ligands.
Scheme 44
Scheme 44
Buchwald's synthesis of DAPH analogues.
Scheme 45
Scheme 45
4SC study of aromatic amination.
Scheme 46
Scheme 46
Movassaghi's pyrrole couplings.
Scheme 47
Scheme 47
Kerr's studies on the CC-1065 CPI subunit.
Scheme 48
Scheme 48
Hosokowa and Tatsuka's synthesis of trichostatin.
Scheme 49
Scheme 49
Bringmann's synthesis of anchisheynine.
Scheme 50
Scheme 50
Novartis synthesis of rocaglamide analogues.
Scheme 51
Scheme 51
Chida's synthesis of murrastifoline A
Scheme 52
Scheme 52
Porco and Panek's synthesis of a library of diketopiperazines.
Scheme 53
Scheme 53
Crich's synthesis of mannosylerythritol lipid A.
Scheme 54
Scheme 54
Seeberger's synthesis of gp120 oligosaccharide.
Scheme 55
Scheme 55
Lakshman's modification 2’-deoxyadenosine derivatives.
Scheme 56
Scheme 56
Rizzo's C8 modified nucleosides.
Scheme 57
Scheme 57
Hocek's synthesis of pyridin-3-yl C-nucleosides.
Scheme 58
Scheme 58
Rhodia study of benzophenone hydrazone arylation.
Scheme 59
Scheme 59
Pfizer synthesis of Torcetrapib.
Scheme 60
Scheme 60
Maes’ development of microwave conditions.
Scheme 61
Scheme 61
Rozman's synthesis of phenothiazines under microwave conditions.
Scheme 62
Scheme 62
Buchwald's amination of aryl nonaflates under microwave conditions.
Scheme 63
Scheme 63
Turner's synthesis of oxindoles by cyclization.
Scheme 64
Scheme 64
Zhu's synthesis of oxindoles by Ugi 4 component coupling.
Scheme 65
Scheme 65
Solvay 3-aminoestrone synthesis.
Scheme 66
Scheme 66
GlaxoSmithKline sulfonamide synthesis under microwave conditions.
Scheme 67
Scheme 67
AstraZeneca synthesis of N-aryl sulfamides.
Scheme 68
Scheme 68
Procter's synthesis of fluorous tagged heterocycles.
Scheme 69
Scheme 69
GlaxoSmithKline synthesis of CRF1 receptor antagonists.
Scheme 70
Scheme 70
Amgen synthesis of vanilloid receptor antagonists.
Scheme 71
Scheme 71
Holmes’ amination of aryl halides in supercritical carbon dioxide.
Scheme 72
Scheme 72
Buchwald's application of solid-supported of a dialkylbiaryl phosphine in aryl chloride amination.
Scheme 73
Scheme 73
Kobayashi's use of polymer-incarcerated palladium with dialkylbiaryl phosphine ligands.
Scheme 74
Scheme 74
Amination of solid supported heteroaryl chlorides.
Scheme 75
Scheme 75
Stang's synthesis of precursors for self-assembling supramolecules.
Scheme 76
Scheme 76
Bolm's synthesis of triazacyclononane derivatives.
Scheme 77
Scheme 77
Lippard's synthesis of fluorescent zinc sensors.
Scheme 78
Scheme 78
Lippard's synthesis of substituted rhodamine fluorophores.
Scheme 79
Scheme 79
Johansson's synthesis of ruthenium(II) ligands.
Scheme 80
Scheme 80
Schrock's synthesis of alkene polymerization catalysts.
Scheme 81
Scheme 81
Buchwald's synthesis of polyaniline.
Scheme 82
Scheme 82
Meyer's synthesis of a polyaniline copolymer.
Scheme 83
Scheme 83
Nozaki's synthesis of heteroacenes.
Scheme 84
Scheme 84
Kawashima's synthesis of azaborines.
Scheme 85
Scheme 85
Synthesis of TPD by selective arylation of ammonia.
Scheme 86
Scheme 86
Meijer's synthesis of poly(aminophthalimide) oligomers.
Scheme 87
Scheme 87
Burgess's synthesis of squaraine-based energy transfer systems.
Scheme 88
Scheme 88
Yang's synthesis of aminostilbenes for studies on charge transfer.
Scheme 89
Scheme 89
Lützen's synthesis of derivatives of 9,9’-spirobifluorenes.
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