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Review
. 2011 Mar 9;111(3):1846-913.
doi: 10.1021/cr1002744. Epub 2011 Jan 14.

Transition metal-catalyzed decarboxylative allylation and benzylation reactions

Jimmie D Weaver  1 , Antonio Recio 3rd, Alexander J Grenning, Jon A Tunge
Affiliations
Review

Transition metal-catalyzed decarboxylative allylation and benzylation reactions

Jimmie D Weaver et al. Chem Rev. .

Abstract

A review. Transition metal catalyzed decarboxylative allylations, benzylations, and interceptive allylations are reviewed.

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Figures

Scheme 1
Scheme 1
Standard Cross-coupling vs. Decarboxylative Coupling
Scheme 2
Scheme 2
Formation of Mercury Enolate via Decarboxylation
Scheme 3
Scheme 3
Effect of Substitution on Allylation vs. Elimination
Scheme 4
Scheme 4
Regioconvergent DcA: Evidence for Pd-π-Allyl Intermediates
Scheme 5
Scheme 5
Regiospecific DcA
Scheme 6
Scheme 6
Kinetic γ-Allylation of Valerolactones
Scheme 7
Scheme 7
Regiospecificity in the DcA of Allyl Enol Carbonates
Scheme 8
Scheme 8
Regioselectivity of the Ru-Catalyzed DcA of β-Ketoesters
Scheme 9
Scheme 9
Comparison of DcA and Traditional 2-Step Method
Scheme 10
Scheme 10
Superior ee’s with an Electron Deficient PHOX Ligand
Scheme 11
Scheme 11
DcA of Vinylogous Ester Enolates
Scheme 12
Scheme 12
Matched/Mismatched Asymmetric DcA
Scheme 13
Scheme 13
Diverse Reactivity of Protected Hydroxy Ketones
Scheme 14
Scheme 14
Regioconvergent, Enantioselective DcA of α-Hydroxy Aldehydes
Scheme 15
Scheme 15
Mechanism of Racemization
Scheme 16
Scheme 16
Ionization of Allyl Carboxylates
Scheme 17
Scheme 17
Decarboxylation Prior to Allylation
Scheme 18
Scheme 18
Allylation Before Decarboxylation
Scheme 19
Scheme 19
Evidence for Allylation Prior to Decarboxylation
Scheme 20
Scheme 20
Evidence for an Outer-sphere Allylation
Scheme 21
Scheme 21
Hypothetical Allylation Prior to Decarboxylation
Scheme 22
Scheme 22
Potential Mechanisms for Decarboxylation
Scheme 23
Scheme 23
Ambiguous Results of a Typical Crossover Experiment
Scheme 24
Scheme 24
Acidic Additives in DcA of an Enol Carbonate
Scheme 25
Scheme 25
Current Mechanistic Understanding
Scheme 26
Scheme 26
Synthesis of trospectomycin sulfate
Scheme 27
Scheme 27
Synthesis of (±)-jiadifenin
Scheme 28
Scheme 28
Synthesis of (±)-lycopladine A
Scheme 29
Scheme 29
Outcome of Annulation/DcA
Scheme 30
Scheme 30
Diels-Alder/DcA
Scheme 31
Scheme 31
Synthesis of spirotryprostatin B
Scheme 32
Scheme 32
Synthesis of (+)-R-dichronanone
Scheme 33
Scheme 33
Synthesis of (−)-cyanthiwigin
Scheme 34
Scheme 34
Syntheses of (+)-cassiol and of (+)-carrisone
Scheme 35
Scheme 35
Synthesis of (+)-Elatol
Scheme 36
Scheme 36
DcA of Amino Acid Derivatives
Scheme 37
Scheme 37
Proposed Mechanism for the DcA of α-Imino Esters
Scheme 38
Scheme 38
Regioconvergent DcA of α-Imino Allyl Esters
Scheme 39
Scheme 39
C- vs. O-allylation
Scheme 40
Scheme 40
Proposed Mechansim for the DcA of Heteroaromatic Allyl Acetic Esters
Scheme 41
Scheme 41
Rationale for Linear and Branched Products
Scheme 42
Scheme 42
Access to Thermodynamically Unfavorable Nucleophiles
Scheme 43
Scheme 43
Pd(0)-catalyzed Allylation/Cope Rearrangement
Scheme 44
Scheme 44
α-Sulfonyl Esters: Surrogates of Hydrocarbon DcA
Scheme 45
Scheme 45
Regiospecificity of the Anion
Scheme 46
Scheme 46
Outer-sphere DcA
Scheme 47
Scheme 47
Qualitative Correlation between Stability and Rate
Scheme 48
Scheme 48
Orgin of Enantiospecificity
Scheme 49
Scheme 49
DcA of Silyl Enol Ethers: Synthesis of Velloziolone
Scheme 50
Scheme 50
DcA of Allyl Propiolates
Scheme 51
Scheme 51
Two Potential Mechanisms
Scheme 52
Scheme 52
Correlation of Mechanism to pKa of Corresponding Amine
Scheme 53
Scheme 53
DcA en Route to Swainsonine
Scheme 54
Scheme 54
Decarboxylative Ring Contraction
Scheme 55
Scheme 55
DcA: an Outer-sphere Process
Scheme 56
Scheme 56
Preferential Formation of 4-Membered Ring
Scheme 57
Scheme 57
Enantioenriched Allyl Selenides are Useful Intermidiates
Scheme 58
Scheme 58
Decarboxylative Michael Addition and Allylation
Scheme 59
Scheme 59
Proposed Mechanism for IDcA
Scheme 60
Scheme 60
Ruthenium-Catalyzed Decarboxylative Insertion of Electrophiles
Scheme 61
Scheme 61
Asymmetric IDcA of Cyclic β-Ketoesters
Scheme 62
Scheme 62
Proposed Cycle for Asymmetric IDcA
Scheme 63
Scheme 63
Proposed Mechanism for Decarboxylative [4+2] Cycloadditions
Scheme 64
Scheme 64
Decarboxylative Cycloadditions with Isocyanates
Scheme 65
Scheme 65
Isotopic labeling experiments
Scheme 66
Scheme 66
Origin of Enantioselectivity: Formation of δ-Lactams
Scheme 67
Scheme 67
Decarboxylative Cycloaddition with Dicyanocyclopropane and N-tosyl Aziridines
Scheme 68
Scheme 68
Proposed Catalytic Cycle for Cycloheptane Formation
Scheme 69
Scheme 69
IDcA of Amino Acid Esters
Scheme 70
Scheme 70
Proposed Catalytic Cycle for IDcA
Scheme 71
Scheme 71
Interception of palladium acetylides
Scheme 72
Scheme 72
Proposed Catalytic Cycles for IDcA of Allylic Alkynoates
Scheme 73
Scheme 73
Proposed Mechanism for Decarboxylative Carbonylation
Scheme 74
Scheme 74
Rationale for Observed Stereochemistry for the Decarboxylative Carbonylation
Scheme 75
Scheme 75
Decarboxylative Isocyanation
Scheme 76
Scheme 76
Rationale for Observed Diastereoselecitivites
Scheme 77
Scheme 77
Proposed Mechanism for Decarboxylative Alkoxyallylation
Scheme 78
Scheme 78
Decarboxylative Carbonylation of Cyclic Vinyl Carbamates
Scheme 79
Scheme 79
Decarboxylative Carbonylation of Cyclic Vinyl Carbamates
Scheme 80
Scheme 80
Proposed Catalytic Cycle for Decarboxylative Carbonylation
Scheme 81
Scheme 81
Diastereoselective Cycloadditions of Vinyl Oxazinones
Scheme 82
Scheme 82
Stereochemical Rationale
Scheme 83
Scheme 83
Interception with 3-Cyanocoumarin
Scheme 84
Scheme 84
Catalytic Cyclic for IDcA of Propargyl Carbonates
Scheme 85
Scheme 85
Comparison of π-Benzyl Substitution Reactions
Scheme 86
Scheme 86
Relative Rates of Palladium π-Allyl/Benzyl Formation
Scheme 87
Scheme 87
Decarboxylative Benzylation of aza-Allyl Anions
Scheme 88
Scheme 88
Palladium-Catalyzed Benzylation of Propiolic Acids
Chart 1
Chart 1
Tsuji-Saegusa Decarboxylative Allylation
Chart 2
Chart 2
DcA of α-Phenyl Diallyl Malonates
Chart 3
Chart 3
Hexadiene Synthesis via DcA
Chart 4
Chart 4
Decarboxylative Cyclization of Valerolactones
Chart 5
Chart 5
DcA of Allyl Enol Carbonates
Chart 6
Chart 6
The First Enantioselective DcA of Ketones
Chart 7
Chart 7
Enantioselective DcA of Allyl Vinyl Carbonates
Chart 8
Chart 8
Select Examples of the AREA Reaction
Chart 9
Chart 9
Enantioselective DcA of α-Fluoro-β-ketoesters
Chart 10
Chart 10
Enantioselective DcA of Z-Enol Carbonates
Chart 11
Chart 11
Enantioselective DcA of 2-Acyl Imidazoles
Chart 12
Chart 12
Scope of DcA of α-Protected Hydroxy Allyl Vinyl Carbonates
Chart 13
Chart 13
Representations of Calculated Transition States
Chart 14
Chart 14
DcA of Allyl Nitroacetic Esters
Chart 15
Chart 15
DcA of Nitroarene Allyl Acetic Esters
Chart 16
Chart 16
DcA of α-Heteroaromatic Acetic Allyl Esters
Chart 17
Chart 17
DcA of α-Cyano Allyl Acetic Esters
Chart 18
Chart 18
DcA of Vinylogous Malononitriles
Chart 19
Chart 19
DcA of α-Sulfonyl Allyl Esters
Chart 20
Chart 20
Stereospecific DcA α-Sulfonyl Esters
Chart 21
Chart 21
DcA of 3-Carboxylcoumarins
Chart 22
Chart 22
DcA of Heteroaromatics
Chart 23
Chart 23
DcA of Allyl Propiolic Esters
Chart 24
Chart 24
Substrates Unfit for DcA
Chart 25
Chart 25
Decarboxylative Allylic Amination
Chart 26
Chart 26
DcA of Heteroaromatic Amines
Chart 27
Chart 27
Scope of the Azetidine Formation
Chart 28
Chart 28
Enantioselective Decarboxylative Allylic Amidation
Chart 29
Chart 29
Enantiospecific Decarboxylative Allylic Amidation
Chart 30
Chart 30
Pd-Catalyzed DcA of Aryl Allyl Carbonates
Chart 31
Chart 31
Ru-Catalyzed Asymmetric DcA of Allyl Aryl Carbonates
Chart 32
Chart 32
Fe-Catalyzed DcA of Allyl Aryl Carbonates
Chart 33
Chart 33
Decarboxylative Allylic Selenation
Chart 34
Chart 34
Decarboxylative β-Acetonation α-Allylation
Chart 35
Chart 35
Regioselective Decarboxylative Formation of Spiro[2.4]heptanes
Chart 36
Chart 36
Asymmetric Generation of Lactams
Chart 37
Chart 37
Piperidine-3-Carboxylic Acids via Decarboxylation of γ-Methylidene-δ-Valerolactones
Chart 38
Chart 38
Decarboxylative Synthesis of Functionalized 1,2-Oxazepines
Chart 39
Chart 39
Cyclopentenimines via Decarboxylation of γ-Methylidene-δ-Valerolactones
Chart 40
Chart 40
IDcA of Allyl Diphenylglycinates
Chart 41
Chart 41
IDcA of Allylic Alkynoates with Benzynes
Chart 42
Chart 42
γ-Butyrolactones via Decarboxylative Carbonylation
Chart 43
Chart 43
Palladium-Catalyzed Decarboxylative Carbamate Formations
Chart 44
Chart 44
Decarboxylative Carbonylation of Allyl Carbamates
Chart 45
Chart 45
Dihydropyridinones via Decarboxylation of Vinyloxazolidinones
Chart 46
Chart 46
Decarboxylative [3+2] Cycloaddition with Activated Olefins
Chart 47
Chart 47
Rationale for Observed Diastereoselectivity
Chart 48
Chart 48
Diastereo- and Enantioselective Decarboxylative Cycloaddition
Chart 49
Chart 49
α-Allyl-β-amino Chromones
Chart 50
Chart 50
Yamamoto’s Proposed Stereochemical Rationale
Chart 51
Chart 51
Palladium-Catalyzed Decarboxylative Synthesis of Dihydrofurans
Chart 52
Chart 52
Decarboxylative Benzylation of Phenols
Chart 53
Chart 53
Select Examples of Benzylated α-Imino Anions
Chart 54
Chart 54
Decarboxylative Coupling of Benzyl Propioliate and β-Keto Esters
Chart 55
Chart 55
Decarboxylative Coupling of Benzyl Propioliates
Chart 56
Chart 56
Palladium-Catalyzed Benzylation of Propiolic Acids
Chart 57
Chart 57
Decarboxylative Coupling of Benzyl β-Keto Esters
Chart 58
Chart 58
Regiospecific Decarboxylative Benzylation
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