Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2011 Apr 13;111(4):2981-3019.
doi: 10.1021/cr100371y. Epub 2011 Mar 23.

Palladium(II)-catalyzed alkene functionalization via nucleopalladation: stereochemical pathways and enantioselective catalytic applications

Richard I McDonald  1 , Guosheng Liu, Shannon S Stahl
Affiliations
Review

Palladium(II)-catalyzed alkene functionalization via nucleopalladation: stereochemical pathways and enantioselective catalytic applications

Richard I McDonald et al. Chem Rev. .
No abstract available

PubMed Disclaimer

Figures

Figure 1
Figure 1
Catalyst: (IMes)Pd(O2CCF3)2(OH2). Na2CO3 (2 equiv), AcOH (0.2 equiv), BzOH (0.2 equiv), p-NO2C6H4CO2H (0.2 equiv), trifluoroacetic acid (1 equiv). The pKa value of additives (in parentheses) was determined in H2O.
Figure 2
Figure 2
Bimetallic PdII-Catalysts for Hydroxy-Chlorination of Alkenes.
Figure 3
Figure 3
Bimetallic PdII-Catalysts for Dibromination of Alkenes.
Scheme 1
Scheme 1
The Wacker Reaction.
Scheme 2
Scheme 2
Versatility of the PdII-Alkyl Intermediate Arising from Alkene Nucleopalladation.
Scheme 3
Scheme 3
Stereochemical Pathways of Nucleopalladation.
Scheme 4
Scheme 4
Analysis of Phenoxypalladation Stereochemistry Using BOXAX Ligands.
Scheme 5
Scheme 5
Mechanistic Basis for the Observed Products Following Cyclization of cis-3-d-6.
Scheme 6
Scheme 6
Observation of trans-Oxypalladation Products at High [Cl−].
Scheme 7
Scheme 7
Mechanistic Explanation for the Formation of 3-d-12.
Scheme 8
Scheme 8
Carboxylic Acid Cyclization Proceeds Exclusively via trans-Oxypalladation.
Scheme 9
Scheme 9
Alcohol Cyclization Proceeds Exclusively via cis-Oxypalladation.
Scheme 10
Scheme 10
Mechanistic Proposal for the Alkoxyarylation of Alkenes.
Scheme 11
Scheme 11
Alkoxyarylation of Deuterated Substrates.
Scheme 12
Scheme 12
Mechanistic Explanation for the Formation of 24, 25, and 26.
Scheme 13
Scheme 13
Divergent Alkoxyarylation Stereochemical Outcomes by Variation of the Achiral Ligand.
Scheme 14
Scheme 14
Mechanistic Hypothesis for the Formation of 33 and 34.
Scheme 15
Scheme 15
Stoichiometric Studies of the Addition of Amine Nucleophiles to Pd-Coordinated Alkenes.
Scheme 16
Scheme 16
Mechanistic Proposal Accounting for the Reaction Outcome in the Aminoarylation of 48.
Scheme 17
Scheme 17
Divergent Aminoarylation Stereochemical Outcomes by Variation of the Achiral Ligand.
Scheme 18
Scheme 18
Proposed Mechanism for the Intramolecular Aminoarylation of Allyl Amines.
Scheme 19
Scheme 19
Intermolecular Oxidative Amination of Norbornene.
Scheme 20
Scheme 20
Mechanistic Rational for the Formation of Products 74–77.
Scheme 21
Scheme 21
Aerobic Oxidative Amination at High [Cl−].
Scheme 22
Scheme 22
Mechanistic Explanation for the Formation of (Z)-88.
Scheme 23
Scheme 23
Alternative Proposal for the Formation of (Z)-88.
Scheme 24
Scheme 24
Insertion of Ethylene into a Pd-Amide Bond.
Scheme 25
Scheme 25
Stereochemistry of Ethylene Insertion into a Pd-Amide Species.
Scheme 26
Scheme 26
Alkene Difunctionalization Reactions.
Scheme 27
Scheme 27
Possible Stereochemical Pathways for Alkene Difunctionalization Reactions.
Scheme 28
Scheme 28
Proposed Mechanism for the Intermolecular Aminoacetoxylation of Alkenes.
Scheme 29
Scheme 29
Mechanistic Rational for the Formation of (Z)-93 via Oxidative Amination of 92.
Scheme 30
Scheme 30
Alkene Difunctionalization in the Presence of N-Fluorobenzenesulfonimide.
Scheme 31
Scheme 31
Trapping an Aminopalladation Intermediate with Bipyridine.
Scheme 32
Scheme 32
Proposed Mechanism for the Rearrangement of Allylic Imidates.
Scheme 33
Scheme 33
Formation of a Pd-Imidate Species.
Scheme 34
Scheme 34
Mechanistic Explanation for the Formation of cis-3,4-d2-103.
Scheme 35
Scheme 35
Mechanistic Hypothesis for the Formation of cis-d-116.
Scheme 36
Scheme 36
Proposed Mechanism for the Oxidative Annulation of Indoles.
Scheme 37
Scheme 37
Mechanistic Explanation for the Formation of cis-126.
Scheme 38
Scheme 38
Evidence for cis-Aminopalladation in a Stoichiometric Carbopalladation Reaction.
Scheme 39
Scheme 39
Enantioselective Phenol Cyclization Using the Chiral Alkene β-Pinene.
Scheme 40
Scheme 40
The Effect of para-Substitution on Yield and Enantioselectivity.
Scheme 41
Scheme 41
Binaphthyl-Derived Bisoxazoline Ligands (BOXAX) for Enantioselective Oxidative Phenol Cyclization Onto Tetrasubstituted Alkenes.
Scheme 42
Scheme 42
Phenol Cyclization onto Trisubstituted Alkenes.
Scheme 43
Scheme 43
a) Chelation-Induced Axially Chiral Bisoxazoline Ligands and b) Their Application to Enantioselective Phenol Cyclization.
Scheme 44
Scheme 44
Aerobic Enantioselective Phenol Cyclization Using (−)-Sparteine.
Scheme 45
Scheme 45
Ligand Screen for Aerobic Phenol Cyclization.
Scheme 46
Scheme 46
Phenol Cyclization Yields Pd-Alkyl Species that Terminate by β-Hydride Elimination or are Trapped by Alkenes or CO.
Scheme 47
Scheme 47
Enantioselective Oxidative Oxycarbonylation as the Key Step in the Asymmetric Total Synthesis of α-Tocopherol.
Scheme 48
Scheme 48
Enantioselective Oxidative Oxycarbonylation.
Scheme 49
Scheme 49
Phenol Oxypalladation/β-Hydride Elimination to Afford Six-Membered Rings.
Scheme 50
Scheme 50
Intermolecular Addition of Phenols to (Z)-Allylic Trichloroacetimidates.
Scheme 51
Scheme 51
Addition of Phenols to (E)-Allylic Trichloroacetimidates.
Scheme 52
Scheme 52
Addition of Carboxylic Acids to (Z)-Allylic Trichloroacetimidates.
Scheme 53
Scheme 53
Enantioselective Oxidative Cyclization of Primary Alcohols.
Scheme 54
Scheme 54
Alkoxy Alkylation of Primary Alcohols.
Scheme 55
Scheme 55
Intramolecular Oxycarbonylation of Primary Alcohols.
Scheme 56
Scheme 56
Cyclization of β-Dicarbonyl Nucleophiles.
Scheme 57
Scheme 57
Intermolecular Alkoxyvinylation of Vinyl Ethers.
Scheme 58
Scheme 58
Difunctionalization of ortho-Vinyl Phenols via a Quinine Methide Intermediate.
Scheme 59
Scheme 59
Intermolecular Dialkoxylation of ortho-Vinyl Phenols.
Scheme 60
Scheme 60
Intramolecular Difunctionalization of ortho-Vinyl Phenols.
Scheme 61
Scheme 61
Synthesis of Traditional Wacker Products or Chlorohydrin Derivatives.
Scheme 62
Scheme 62
Hydroxy-Chlorination Using Monometallic Catalysts.
Scheme 63
Scheme 63
Hydroxy-Chlorination Using Bimetallic Catalysts.
Scheme 64
Scheme 64
The First PdII-Catalyzed Enantioselective Allylic Imidate Rearrangement.
Scheme 65
Scheme 65
Enantioselective Allylic Trichloroacetimidate Rearrangement.
Scheme 66
Scheme 66
Intramolecular C–N Bond-Forming Allylic Substitution.
Scheme 67
Scheme 67
COP–X Catalyzed Enantioselective Aminopalladation/β-Hydride Elimination.
Scheme 68
Scheme 68
Enantioselective Hydroamination of Styrenes
Scheme 69
Scheme 69
Proposed Mechanism for Styrene Hydroamination.
Scheme 70
Scheme 70
Aminocarbonylation of Sulfonamides.
Scheme 71
Scheme 71
Aminocarbonylation of N-Tosyl Ureas.
Scheme 72
Scheme 72
Aminocarbonylation of Amino Alcohols.
Scheme 73
Scheme 73
Aerobic Oxidative Aminovinylation.
Scheme 74
Scheme 74
Aerobic Oxidative Aminovinylation with Chiral PdII-NHC Complexes.
Scheme 75
Scheme 75
Ligand Screen for Aerobic Oxidative Aminovinylation.
Scheme 76
Scheme 76
Screen of Chiral Phosphine Ligands.
Scheme 77
Scheme 77
Enantioselective Aminoarylation with Aryl and Vinyl Halides.
Scheme 78
Scheme 78
Proposed Mechanism for Alkene Diamination with Di-tert-butyldiaziridinone.
Scheme 79
Scheme 79
Pd0-Catalyzed Diamination of Terminal Alkenes.
Scheme 80
Scheme 80
Aerobic Oxidative Amination with Chiral PdII-NHC Complexes.
Scheme 81
Scheme 81
Aerobic Oxidative Amination of ortho-Allyl Tosylanilides.
Scheme 82
Scheme 82
Enantioselective Fujiwara-Moritani Cross-Coupling.
Scheme 83
Scheme 83
Aerobic Oxidative Annulation of Indoles.
Scheme 84
Scheme 84
General Mechanism for the Oxidative Heck Reaction.
Scheme 85
Scheme 85
Aerobic Oxidative Heck Cross-Coupling of Aryl Boronic Acids and α,β-Unsaturated Esters.
Scheme 86
Scheme 86
Aerobic Oxidative Heck Cross-Coupling of an Aryl Boronic Acid and Vinyl Ether. aWith MeOBiphep
Scheme 87
Scheme 87
Intramolecular Aerobic Oxidative Heck Reaction.
Scheme 88
Scheme 88
Aerobic Oxidative Heck Cross-Coupling of Phenyl Boronic Acids and α,β-Unsaturated Aldehydes.
Scheme 89
Scheme 89
Tridentate NHC-Amidate-Alkoxide Ligands in Aerobic Oxidative Heck Cross-Coupling.
Scheme 90
Scheme 90
PdII-Catalyzed Arylation of Alkenes.
Scheme 91
Scheme 91
1,4-Addition of Triarylbismuths to α,β-Unsaturated Carbonyls.
Scheme 92
Scheme 92
Conjugate Addition of Triarylbismuths, Aryl Potassium Trifluoroborates, and Aryl Trifluorosilicates to Enones. aCu(BF4)2·6H2O (0.76 equiv relative to enone). bZnF2 (1 equiv).
Scheme 93
Scheme 93
Conjugate Addition of Aryl Boronic Acids to Enones.
Scheme 94
Scheme 94
Hydrosilylation/Cyclization of 1,6-Dienes.
Scheme 95
Scheme 95
Hydrosilylation/Cyclization Using Various Silanes.
Scheme 96
Scheme 96
Proposed Mechanism for Acetoxylation/Cyclization.
Scheme 97
Scheme 97
Chiral Ligand Screen for Enantioselective Carbocyclization.
Scheme 98
Scheme 98
Acetoxylation/Cyclization with the Pd(TFA)2/SPRIX Catalyst.
Scheme 99
Scheme 99
Proposed Mechanism for the Synthesis of Cyclopropanes via Oxidative Cyclization of Enynes.
Scheme 100
Scheme 100
Ligand Screen for the Oxidative Cyclization of Enynes.
Scheme 101
Scheme 101
Dibromination Using Bimetallic Catalysts.
See this image and copyright information in PMC

References

    1. Smidt J, Hafner W, Jira R, Sedlmeier S, Sieber R, Rüttinger R, Kojer H. Angew. Chem. 1959;71:176.
    2. Smidt J, Hafner W, Jira R, Sieber R, Sedlmeier S, Sabel A. Angew. Chem., Int. Ed. 1962;1:80.
    3. Jira R. Angew. Chem. Int. Ed. 2009;48:9034. - PubMed

    1. For recent reviews of the Wacker process, see: Takacs JM, Jiang X. Curr. Org. Chem. 2003;7:369. Cornell CN, Sigman MS. Inorg. Chem. 2007;46:1903. Muzart J. Tetrahedron. 2007;63:7505.

    1. Keith JA, Henry PM. Angew. Chem., Int. Ed. 2009;48:9038. - PubMed
    1. Phillips FC. Am. Chem. J. 1894;16:255.

    1. For reviews, see: Henry PM. Palladium Catalyzed Oxidation of Hydrocarbons. Vol. 2. Metal Complexes; D. Reidel Publishing Co.; Dordrecht: 1980. Bäckvall JE. Acc. Chem. Res. 1983;16:335. Negishi E, editor. Handbook of Organopalladium Chemistry for Organic Synthesis. Vol. 2. Wiley; New York: 2002. Jira R. In: Applied Homogeneous Catalysis with Organometallic Compounds. Weinheim. 2nd ed. Cornils B, Herrmann WA, editors. Wiley-VCH; 2002. p. 386. Sigman MS, Schultz MJ. Org. Biomol. Chem. 2004;2:2551. Stoltz BM. Chem. Lett. 2004;33:362. Tietze LF, Ila H, Bell HP. Chem. Rev. 2004;104:3453. Minatti A, Muniz K. Chem. Soc. Rev. 2007;36:1142. Kotov V, Scarborough CC, Stahl SS. Inorg. Chem. 2007;46:1910. Beccalli EM, Broggini G, Martinelli M, Sottocornola S. Chem. Rev. 2007;107:5318. Jensen KH, Sigman MS. Org. Biomol. Chem. 2008;6:4083. Gligorich KM, Sigman MS. Chem. Commun. 2009:3854.

Publication types