Table of Contents
Title Page
Copyright
Introduction and Preface
References
Chapter 1: Functionalization of Heteroaromatic Substrates using Groups 9 and 10 Catalysts
1.1 Introduction
1.2 Thiophenes, furans, and Related Heterocycles
1.3 Pyrroles, Indoles, Pyridines, and Imidazopyridines
1.4 Azoles and Other Miscellaneous Heterocycles
1.5 Summary
References
Chapter 2: Ruthenium Catalysts for the Alkylation of Functionalized Arenes and Heteroaromatic Substrates via Hydroarylation
2.1 Introduction
2.2 Alkylation by Ruthenium(0) Catalysts via Oxidative-Addition C
H Activation
2.3 Summary and Conclusions
Abbreviations
References
Chapter 3: Alkylation of Arenes Without Chelation Assistance: Transition Metal Catalysts with d6 Electron Configurations
3.1 Transition Metal-Mediated Arene Alkylation: Overview
3.2 Octahedral d
6
Transition Metal Catalysts for Olefin Hydroarylation: Scorpionate Supported Ru(II) Catalysts
3.3 Olefin Hydroarylation Catalyzed by Octahedral d
6
Ir(III) Supported by the Acetylacetonate Ligand
3.4 Summary: Comparison of Ru(II) and Ir(III) Catalysts for Olefin Hydroarylation
3.5 Future Outlook: Extension of Olefin Hydroarylation using Hydrocarbons to Earth Abundant Metals
References
Chapter 4: Hydroarylation of Olefins with Complexes Bearing d8 Metal Centers
4.1 Introduction
4.2 Pt
II
Catalyzed Hydroarylation
4.3 Rh
I
-Catalyzed Hydroarylation
4.4 Directed
ortho
-Hydroarylation Catalyzed by Ir
I
Complexes
4.5 Hydroarylation with Ni
0
Complexes via Ni
II
Intermediates
4.6 Formal Hydroarylation Reactions with Pd
II
Catalysts via Heck-Like Mechanisms
4.7 Conclusions
References
Chapter 5: Hydroarylation of C
C Multiple Bonds Using Nickel Catalysts
5.1 Introduction
5.2 Hydroarylation of Alkynes
5.3 Hydroheteroarylation of Alkynes
5.4 Hydroarylation of Alkenes
5.5 Hydroheteroarylation of Alkenes
5.6 Summary and Outlook
References
Chapter 6: Hydroarylation of Alkynes and Alkenes using Group 7–9 First-Row Transition Metal Catalysts
6.1 Introduction
6.2 Hydroarylation of Alkynes and Alkenes using Cobalt Catalysts
6.3 Hydroarylation of Alkynes and Alkenes using Iron Catalysts
6.4 Hydroarylation of Alkynes using Low-Valent Manganese Catalyst
6.5 Conclusions
6.6 Abbreviations
References
Chapter 7: Hydroarylation of Alkynes using Cu, Ag, and Au Catalysts
7.1 Introduction
7.2 Intramolecular Hydroarylation of Alkynes
7.3 Intermolecular Hydroarylation of Alkynes
7.4 Metal-Supported Catalysts and Their Applications in Hydroarylation of Alkynes
7.5 Hydroarylation of Alkynes in Total Synthesis
References
Chapter 8: 8
8.1 Introduction
8.2 Catalyzed Alkyne Hydroarylations Using Arylboron and Arylsilicon Reagents
8.3 Catalyzed Alkyne Hydroarylations Using Aryl Halides and Arenediazonium Compounds
8.4 Synthetic Applications of Alkyne Hyaroarylations Using Arylboron Reagents and Aryl Halides
8.5 Summary
References
Chapter 9: Transition Metal-Catalyzed Hydroarylation of Allenes
9.1 Introduction
9.2 Intramolecular Hydroarylation
9.3 Intermolecular Hydroarylation
9.4 Enantioselective Hydroarylation
9.5 Summary and Outlook
References
Index
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: Functionalization of Heteroaromatic Substrates using Groups 9 and 10 Catalysts
Figure 1.1 General intermolecular hydroarylation of C
C multiple bonds with (hetero)aromatic substrates and comparison to Friedel–Crafts alkylation.
Figure 1.2 Hydroarylation of alkynes: mechanisms and selectivity of the resulting compounds.
Figure 1.3 Examples of seminal hydroarylation reactions.
Figure 1.4 Hydroarylation of alkynes under Rh catalysis (yields are based on alkyne).
Figure 1.5 Hydroarylation of ethylphenylpropiolate with 2-methylfuran (a) and possible mechanism (b).
Figure 1.6 Reactions between ethylpropiolates and furans.
Figure 1.7 Reactions between ethylpropiolates and thiophenes, and mechanistic proposal.
Figure 1.8 Hydroarylation of ethyl phenylpropiolate using a dicarbene Pd(II) complex.
Figure 1.9 Ni-catalyzed hydroarylation of alkynes.
Figure 1.10 Imine as an effective directing group for the functionalization of benzofuran.
Figure 1.11 Hydroarylation of unactivated alkynes catalyzed by a Pd(II) complex.
Figure 1.12 Intramolecular hydroarylation of alkynoates using Pd(OAc)
2
as the catalyst precursor.
Figure 1.13 Intramolecular hydroarylation of a furan-yne substrate.
Figure 1.14 Synthesis of angelicin derivatives by intramolecular hydroarylation of benzofuran.
Figure 1.15 Intramolecular hydroarylation of 2-(2-ethynylphenyl)thiophene.
Figure 1.16 Intramolecular hydroarylation of terminal enynes catalyzed by PtCl
4
.
Figure 1.17 Intramolecular reactions of furylalkynes catalyzed by PtCl
2
.
Figure 1.18 Hydroarylation of ethylene catalyzed by a bipyridine Pt(II) complex.
Figure 1.19 Examples of hydroarylation of styrene and styrene derivatives.
Figure 1.20 Enantioselective hydroarylation of bicycloalkenes with heteroarenes using an Ir catalyst.
Figure 1.21 Intramolecular hydroarylations affording
Iboga
alkaloid benzofuran analogs using a Ni catalyst.
Figure 1.22 Hydroarylation of alkenes with furan and benzofuran derivatives.
Figure 1.23 Asymmetric hydroarylation of vinyl ethers using an Ir catalyst precursor.
Figure 1.24 Hydroarylation reactions of alkenes and alkynes with 2-(thiophen-2-yl)pyridine.
Figure 1.25 Rh-catalyzed functionalization of 2-(thiophen-2-yl)pyridine.
Figure 1.26 Mechanistic proposal for hydroarylation of alkynes and alkenes catalyzed by an NHC-Rh complex.
Figure 1.27 Hydroarylation of alkynes at the C2 position of a pyrrole using Pd or Pt catalysts.
Figure 1.28 Hydroarylation of alkynes at the C3 position of pyrroles.
Figure 1.29 Intramolecular benzannulation at the C2 position of pyrroles using tethered alkynes.
Figure 1.30 Benzannulation at the C3 position of pyrroles.
Figure 1.31 Hydroarylation of alkynes and alkenes at C2 and C3 positions of pyridines.
Figure 1.32 Hydroarylation of alkynes and alkenes using pyridines.
Figure 1.33 Cyclization of pyridines via intramolecular hydroarylation.
Figure 1.34 Hydroarylation of alkynes at the C2 position of indoles.
Figure 1.35 Hydroarylation of alkynes and allenes at the C3 position of indoles.
Figure 1.36 Hydroarylation of alkenes at the C3 position of indoles.
Figure 1.37 Hydroarylation of alkenes at the C2 position of indoles.
Figure 1.38 Benzannulation at the C2 position of indoles.
Figure 1.39 Benzannulation at the C3 position of indoles.
Figure 1.40 Intramolecular hydroarylation of homoallyl-benzimidazoles using a Rh catalyst.
Figure 1.41 Intermolecular hydroarylation of benzimidazole and related heteroaromatic substrates using a Rh catalyst.
Figure 1.42 Application of intramolecular alkene hydroarylation to the synthesis of high value-added products.
Figure 1.43 Oxazolines and dihydroquinazolines as substrates in hydroarylation reactions catalyzed by Rh complexes.
Figure 1.44 Intramolecular alkene hydroarylation as a key step in the synthesis of Vasicoline.
Figure 1.45 Intermediates in the C
H bond activation of 3,4-dihydroquinazolines using Rh catalysts.
Figure 1.46 Hydroarylation of alkenes using Ni catalysts with control of the regioselectivity.
Figure 1.47 Tandem isomerization–hydroarylation using a Ni catalyst with control of regioselectivity.
Figure 1.48 Enantioselective hydroarylation of electron-poor alkenes using a Rh catalyst.
Figure 1.49 Cobalt-catalyzed hydroarylation of alkynes using azoles.
Figure 1.50 Summary of nickel-catalyzed hydroarylation of alkynes.
Chapter 2: Ruthenium Catalysts for the Alkylation of Functionalized Arenes and Heteroaromatic Substrates via Hydroarylation
Scheme 2.1 Manifolds of ruthenium-catalyzed C
H alkylations.
Scheme 2.2 The first catalytic ruthenium-catalyzed C
H alkylation reaction.
Scheme 2.3 Olefin hydroarylation by the Murai group.
Scheme 2.4 Proposed catalytic cycle via ruthenium(0)-mediated C
H activation through oxidative addition.
Scheme 2.5 Early hydroarylation work using aryl ketones.
Scheme 2.6 The use of ruthenium-catalyzed C
H alkylations in polymer chemistry.
Scheme 2.7 The ruthenium-catalyzed C
H alkylation of the diterpene
8
.
Scheme 2.8 Alkylation of β-C
H bonds in α,β-unsaturated esters by ruthenium(0) catalysis.
Scheme 2.9 Esters
12
as C−H alkylation substrates.
Scheme 2.10 Aldehydes as directing groups.
Scheme 2.11 The
in situ
-generated catalytic system using [RuCl
2
(
p
-cymene)]
2
precatalyst with PPh
3
.
Scheme 2.12 Linear selective C
H alkylation using an
in situ
-generated catalyst.
Scheme 2.13 Further development of ruthenium-catalyzed C
H alkylations using an
in situ
-generated catalyst.
Scheme 2.14 The advantage of using
i
PrOH/acetone as a green solvent medium.
Scheme 2.15 The use of aryl imines in a C
H alkylation reaction.
Scheme 2.16 Catalyst-controlled, site-selective C
H alkylations.
Scheme 2.17 Imidates
24
,
27
and a directing group-dependent change in product selectivity.
Scheme 2.18 Ruthenium(0)-catalyzed hydroarylation with hydrazone starting materials.
Scheme 2.19 Benzonitriles
32
as substrates in the ruthenium(0)-catalyzed C
H alkylation reaction.
Scheme 2.20 An example of a ruthenium(0)-catalyzed C
H alkylation with aniline
34
.
Scheme 2.21 Methylenecyclopropanes
37
as alkylating reagents.
Scheme 2.22 Alkylation of C(sp
3
)
H bonds using Ru
3
(CO)
12
catalyst.
Scheme 2.23 Ruthenium-catalyzed alkylation of C(sp
3
)
H bonds with substituted alkenes.
Scheme 2.24 Alkylation of C(sp
3
)
H bonds using a RuCl
2
(PPh
3
)
3
/
rac
-BINAP catalytic system.
Scheme 2.25 Catalytic cycle via ruthenium(II)-mediated, carboxylate-assisted C
H bond activation.
Scheme 2.26 The first report on carboxylate-assisted, ruthenium(II)-catalyzed C
H alkylations via isohypsic C
H activation.
Scheme 2.27 Carboxylate-assisted alkylations using a bidentate directing group.
Scheme 2.28 Alkylation of benzamides
49
with monodentate DGs by carboxylate assistance.
Scheme 2.29 Carboxylate assistance in hydroarylations of methylenecyclopropanes
37
.
Scheme 2.30 Triphenylphosphine oxide (
51
) in the C
H alkylation reaction.
Scheme 2.31 Triphenylphosphine ligand leading to branched product
55
selectivity.
Scheme 2.32 Arene ligand leading to linear products.
Scheme 2.33 The C
H alkylation of acetophenones
2
using maleimide
57
.
Scheme 2.34 Allene
60
in the ruthenium(II)-catalyzed carboxylate-assisted C
H alkylation reaction.
Chapter 3: Alkylation of Arenes Without Chelation Assistance: Transition Metal Catalysts with d6 Electron Configurations
Figure 3.1 (a) Plot of
k
obs
for stoichiometric C
D activation of C
6
D
6
by TpRu(L)(NCMe)Ph (L = CO, BPhos, SPhos, or PMe
3
) at 60 °C with 0.065 mmol of added NCMe versus reversible Ru(III/II) potentials (vs NHE). (b) Plot of calculated
for ethylene insertion into the Ru
Ph bond from TpRu(L)(η
2
-C
2
H
4
)Ph complexes. Data using
Ru-P(pyr)
3
is not included in the linear regression since this complex decomposes in competition with C
6
D
6
activation.
Figure 3.2 Turnover number as a function of
E
Ru(III/II)
for ethylene hydrophenylation using TpRu(L)(NCMe)Ph catalysts and
Tpm
5
Ru-BPhos
using 0.025 mol% Ru (relative to C
6
H
6
) and 0.1 MPa of ethylene at 90
°
C.
Figure 3.3 Mononuclear Ir(III) complexes used as catalyst precursors for olefin hydroarylation (L = acac refers to C-bound κ
1
ligand).
Figure 3.4 The Ir(III) complex (trop)
2
Ir(py)Ph (trop = κ
2
-
O
,
O
-tropolonato;
Ir-trop
).
Scheme 3.1 Olefin hydroarylation using Friedel–Crafts catalysis (LA = Lewis acid, such as AlCl
3
; HX = Brønsted acid, such as HF or HCl).
Scheme 3.2 General mechanism for transition metal-mediated olefin hydroarylation via a non-acid pathway with possible side reactions.
Scheme 3.3 Hydroarylation of ethylene (0.2 MPa) using 0.1 mol% TpRu(CO)(NCMe)Ph (
Ru-CO
) in benzene or ethylbenzene after 4 h at 90 °C. TOF = turnover frequency ([product]/[
Ru-CO
] × time).
Scheme 3.4 Attempted catalytic hydrophenylation of olefins possessing electron-donating substituents results in C
O or C
S bond cleavage.
Scheme 3.5 Catalytic ethylene hydroarylation with heteroaromatic substrates.
Scheme 3.6 Proposed catalytic cycle for the hydrophenylation of ethylene using
Ru-CO
.
Scheme 3.7 Pathway for the formation of TpRu(L)(η
3
-
C
4
H
7
) (L = PMe
3
, BPhos, and SPhos), the primary mechanism of catalyst deactivation for TpRu(II)-catalyzed ethylene hydrophenylation.
Scheme 3.8 Direct comparison of TO for ethylbenzene using
Tpm
5
Ru-BPhos
and
Ru-BPhos
with 0.1 MPa of ethylene and 0.025 mol% Ru (relative to benzene) at 90 °C.
Scheme 3.9 Hydrophenylation of ethylene using [Ir(μ-acac-
O
,
O
,
C
3
)-(acac-
O
,
O
)-(acac-
C
3
)]
2
(
Ir-acac
) to provide ethylbenzene in a H
2
O-saturated benzene solution (mol% of
Ir-acac
relative to benzene).
Scheme 3.10 Hydrophenylation of substituted olefins using
Ir-acac
(0.003 mol% relative to benzene) at 180 °C.
Scheme 3.11 Hydroarylation of ethylene using
Ir-acac
.
Scheme 3.12 Proposed mechanism for ethylene hydrophenylation catalyzed by
cis
-(κ
2
-
O,O
-acac)
2
Ir(η
2
-C
2
H
4
)Ph.
Scheme 3.13 Product selectivity from the hydrophenylation of substituted olefins is ultimately dictated by the mode of insertion into the Ir
Ph bond.
Scheme 3.14 Comparison of calculated enthalpies (kcal/mol) of activation for ethylene insertion and benzene C
H activation during ethylene hydrophenylation catalyzed by
cis
-(
O,O
-acac)
2
Ir and TpRu(CO) [37].
Scheme 3.15 Examples of aromatic C
H activation mediated by Cp*Fe(Me)(Me-NHC) (Me-NHC = 1,3,4,5-tetramethyl-imidazol-2-yl).
Scheme 3.16 Examples of aromatic C
H activation mediated by Cp*Fe(CO)(NCMe)Ph.
Chapter 4: Hydroarylation of Olefins with Complexes Bearing d8 Metal Centers
Figure 4.1 PyInd-ligated Pt complexes for olefin hydroarylation.
Figure 4.2 Several PyPyr ligated complexes for olefin hydroarylation.
Figure 4.3 Proposed mechanism for (PyPyr)Pt
II
- catalyzed olefin hydroarylation.
Figure 4.4 Calculated barriers for C-H activation with cationic Pt complexes via either a two-step oxidative addition/reductive elimination route (black, solid) or a single-step σ-bond metathesis (gray, dashed) pathway. Energies are given in kcal/mol.
Figure 4.5 Possible mechanisms for cationic Pt
II
-catalyzed hydrophenylation of ethylene. Complex
30
is on the catalytic cycle for mechanism 1 (gray, solid), whereas it is an off-cycle resting state in mechanism 2 (gray, dashed).
Figure 4.6 Alternative ligand designs using a linked bpy motif.
Figure 4.7 Proposed catalytic cycle for the hydroarylation of cyclohexene with mesitylene with complex
46
.
Figure 4.8 Possible reaction pathways for the reaction of a bicyclic olefin with complex
53
in benzene-
d
6
.
No hydroarylation reactions occurred; only the rearrangement product was observed.
Figure 4.9 Complexes of the type [L
2
Pt
II
(THF)Ph][BAr′
4
] and [L
3
Pt
II
(C
2
H
4
)] bearing phosphine, mixed phosphine, or bis-
N
-heterocyclic carbene-based ligands.
Figure 4.10 Mechanism for styrene formation with a Rh
I
hydroarylation-like system.
Figure 4.11 Generalized mechanism for Rh
I
-catalyzed
ortho
-hydroyarlation.
Figure 4.12 Self-assembly of a barbiturate derivative and 2,4,6-triaminopyrimidine with Rh
I
, generating a solid-supported hydroarylation catalyst.
Figure 4.13 Mechanism for intramolecular
ortho
-hydroarylation with Rh
I
.
Figure 4.14 Asymmetric, chiral phosphorous-containing ligands used for enantioselective hydroarylation.
Figure 4.15 Mechanism for quinolylamide-directed
ortho
-hydroarylation.
Figure 4.16 Mechanism for hydroarylation and C-C coupling using a [Rh
I
(OH)] complex.
Figure 4.17 Chiral phosphine ligands used to generate [L
2
CpIr
I
] complexes.
Figure 4.18 Proposed catalytic species for the
ortho
-hydroarylation of norbornene with phenol using dimeric (diphosphine)Ir
I
complexes.
Figure 4.19 Structure of (
R
,
R
)-S-Me-BIPAM,
145
.
Figure 4.20 Calculated barriers for the two possible insertion and reductive elimination routes in
ortho
-hydroarylation using [(dppm)Ir
I
(cod)]
+
as the added catalyst. Olefin insertion into the metal–hydride and subsequent C-C reductive elimination pathway (black, solid) was calculated to have a larger kinetic barrier than the pathway involving arene insertion followed by C-H reductive elimination (gray, dashed). Only the anti-Markovnikov pathways are depicted. All complexes exist as cationic species and the charge has been omitted for clarity. Energies are given in kcal/mol.
Figure 4.21 Deuterium-labeling study with and without NaO
t
Bu using various octene substrates.
Figure 4.22 Proposed mechanism for formate-assisted Pd
II
hydroarylation of substituted norbornenes.
Figure 4.23 Chiral ligands for Pd hydroarylation.
Figure 4.24 Mechanism for aerobic alcohol oxidation coupled to hydroarylation.
Scheme 4.1 General synthesis of PyInd ligands.
Scheme 4.2 Ethane elimination and intermolecular C-H activation with (PyPyr)Pt
IV
complexes at 85–100 °C for 1 day.
Scheme 4.3 Synthesis of cationic [(
t
bpy)Pt
II
PhL]
+
complexes bearing labile ancillary L-type ligands.
Scheme 4.4 Synthesis of Rh
I
complexes of the type [L
2
Rh(olefin)(TFA)].
Scheme 4.5 Synthesis of (+)-lithospermic acid (
108
) via Rh catalyzed hydroarylation.
Scheme 4.6 Total synthesis of mescaline derivative
109
via Rh catalyzed hydroarylation.
Scheme 4.7 Arene C-H(D) activations and H(D) scrambling with Rh
I
complex
123
.
Scheme 4.8 Deuterium-labeling study in oxidatively coupled hydroarylation.
Chapter 5: Hydroarylation of C
C Multiple Bonds Using Nickel Catalysts
Scheme 5.1 Nickel-catalyzed hydroacylation of alkynes.
Scheme 5.2 Nickel-catalyzed hydroalkynylation of alkynes.
Scheme 5.3 Nickel-catalyzed alkylation of imidazolium salts.
Scheme 5.4 Nickel-catalyzed alkylation of heteroarene–BF
3
complexes.
Scheme 5.5 Nickel-catalyzed hydroarylation of alkynes with pentafluorobenzene.
Scheme 5.6 Nickel-catalyzed hydroarylation of 4-octyne with fluoroarenes.
Scheme 5.7 Plausible mechanism of nickel-catalyzed hydroarylation of alkynes proposed based on stoichiometric experiments.
Scheme 5.8 A plausible mechanism of nickel-catalyzed hydroarylation of alkynes proposed based on theoretical calculations.
Scheme 5.9 Nickel-catalyzed hydroheteroarylation of alkynes with indoles.
Scheme 5.10 Nickel-catalyzed hydroheteroarylation of 4-ocytne with five-membered heteroarenes.
Scheme 5.11 Nickel-catalyzed hydroheteroarylation of alkynes with 2-phenyl-1,3,4-oxadiazole.
Scheme 5.12 Nickel/aluminum-catalyzed hydroheteroarylation of alkynes with imidazoles.
Scheme 5.13 Nickel/aluminum-catalyzed hydroheteroarylation of alkynes with 2-substituted imidazoles.
Scheme 5.14 Nickel-catalyzed hydroheteroarylation of alkynes with imidazo[1,5-
a
]pyridines.
Scheme 5.15 Nickel-catalyzed hydroheteroarylation of alkynes with triazolo[1,5-
a
]pyridines.
Scheme 5.16 Nickel-catalyzed hydroheteroarylation of alkynes with azine-
N
-oxides.
Scheme 5.17 Nickel/zinc-catalyzed hydroheteroarylation of alkynes with azines.
Scheme 5.18 Nickel/aluminum-catalyzed hydroheteroarylation of 4-octyne with pyridine.
Scheme 5.19 Nickel/aluminum-catalyzed hydroheteroarylation of 4-octyne with pyridine.
Scheme 5.20 Nickel-catalyzed hydroarylation of 2-vinylnaphthalene with pentafluorobenzene.
Scheme 5.21 Nickel-catalyzed hydroarylation of alkenes with 1,3-bis(trifluoromethyl)benzene.
Scheme 5.22 Plausible mechanism of nickel-catalyzed hydroarylation of alkenes proposed based on theoretical calculations.
Scheme 5.23 Nickel-catalyzed hydroheteroarylation of alkenes with indoles.
Scheme 5.24 Nickel-catalyzed hydroheteroarylation of alkenes with benzofurans.
Scheme 5.25 Nickel-catalyzed hydroheteroarylation of 1-decene with 1-methylpyrrole.
Scheme 5.26 Nickel-catalyzed hydroheteroarylation of alkenes with furans.
Scheme 5.27 Nickel-catalyzed hydroheteroarylation of 2-octene with 1-methylindole.
Scheme 5.28 Nickel-catalyzed hydroheteroarylation of vinylarenes with 1-methylbenzimidazole.
Scheme 5.29 Nickel/aluminum-catalyzed hydroheteroarylation of vinylarenes with 1-methylbenzimidazole.
Scheme 5.30 Nickel-catalyzed hydroheteroarylation of allylbenzene.
Scheme 5.31 Nickel/aluminum-catalyzed hydroheteroarylation of allylarenes with 1-methylbenzimidazole.
Scheme 5.32 Nickel/aluminum-catalyzed hydroheteroarylation of alkenes with azines.
Scheme 5.33 Nickel/aluminum-catalyzed hydroheteroarylation of styrene with pyridine.
Scheme 5.34 Nickel/aluminum-catalyzed hydroheteroarylation of alkenes with imidazo[1,5-
a
]pyridine.
Scheme 5.35 Nickel/aluminum-catalyzed hydroheteroarylation of vinylarenes with imidazo[1,5-
a
]pyridines.
Chapter 6: Hydroarylation of Alkynes and Alkenes using Group 7–9 First-Row Transition Metal Catalysts
Scheme 6.1 Ruthenium-catalyzed, ketone-directed hydroarylation of alkene.
Scheme 6.2 A general catalytic cycle for directing group-assisted hydroarylation of alkenes and alkynes.
Scheme 6.3 Cyclometalation of azobenzene with a Co
I
complex.
Scheme 6.4 Cobalt-catalyzed addition of azobenzene to diphenylacetylene.
Scheme 6.5 A ternary catalytic system for the addition of 2-phenylpyridine to 4-octyne.
Scheme 6.6 Cobalt-catalyzed alkyne hydroarylation reactions.
Scheme 6.7 Products of the cobalt-catalyzed addition of aryl ketimines to diphenylacetylene (Scheme 6.6a).
Scheme 6.8 Products of the cobalt-catalyzed addition of
N
-pyrimidylindole to unsymmetrically substituted alkynes (2-pym = 2-pyrimidyl; r.r. = regioisomer ratio; Scheme 6.6c).
Scheme 6.9 Possible catalytic cycle for the addition of aryl ketimine to alkyne (R
L
and R
S
denote larger and smaller substituents, respectively).
Scheme 6.10 Co(PMe
3
)
4
-catalyzed addition of aryl ketimine to diphenylacetylene.
Scheme 6.11 Concerted C-H activation/hydrogen transfer mechanism.
Scheme 6.12 Cobalt-catalyzed addition of oxazole and thiazole derivatives to internal alkynes.
Scheme 6.13 Cobalt-catalyzed, ligand-controlled regiodivergent addition of 2-phenylpyridine to styrene.
Scheme 6.14 Proposed catalytic cycles for the regiodivergent addition of 2-phenylpyridine to styrene.
Scheme 6.15 Branch-selective addition of aryl aldimine and ketimine to styrene under cobalt–triarylphosphine catalysis.
Scheme 6.16 Enantioselective addition of 1-Boc-3-iminoindole to styrene derivative with a cobalt–phosphoramidite catalyst.
Scheme 6.17 Linear-selective addition of aryl ketimine to styrene under cobalt–triarylphosphine catalysis.
Scheme 6.18 Transition state models for the linear-selective addition of aryl ketimine to styrene.
Scheme 6.19 Cobalt-catalyzed, amide-directed hydroarylation of alkenes.
Scheme 6.20 Imine-directed hydroarylation of vinylsilane and alkyl olefin using cobalt–phenanthroline-type catalysts.
Scheme 6.21 Imine-directed intramolecular olefin hydroarylation on an indole platform.
Scheme 6.22 Tandem alkene isomerization–hydroarylation reaction.
Scheme 6.23 Cobalt-catalyzed C4-alkylation of pyridine with alkenes.
Scheme 6.24 Cp*Co
III
-catalyzed, directing group-assisted hydroarylation of alkene and alkyne.
Scheme 6.25 Cyclometalation of aryl imines with Fe
0
and Fe
II
complexes.
Scheme 6.26 Addition of 3-iminoindole to aryl olefins and alkynes under iron–NHC catalysis.
Scheme 6.27 FeCl
3
-catalyzed hydroarylation of styrenes with electron-rich arenes.
Scheme 6.28 Stoichiometric cyclometalation of MnBn(CO)
5
and subsequent alkyne insertion.
Scheme 6.29 Manganese-catalyzed directed hydroarylation of terminal alkynes.
Scheme 6.30 Manganese-catalyzed directed hydroarylation of α,β-unsaturated carbonyl compounds.
Chapter 7: Hydroarylation of Alkynes using Cu, Ag, and Au Catalysts
Figure 7.1 Salts and complexes of gold, silver, and copper used in alkyne hydroarylation.
Figure 7.2 Examples of fused and spirocyclic compounds, which were assembled through gold-catalyzed intramolecular hydroarylation/iminium trapping cascade strategy.
Figure 7.3 Ligands employed in enantioselective gold-catalyzed synthesis of dihydropyranyl indolines and dihydrofuranyl indolines.
Figure 7.4 Scope of the phenol synthesis via furan–ynes intramolecular alkyne hydroarylation.
Figure 7.5 Examples of natural compounds, synthesized by gold-catalyzed hydroarylation of alkynes.
Scheme 7.1 Metal-catalyzed hydroarylation of alkynes.
Scheme 7.2 Gold-catalyzed hydroarylation for the synthesis of dihydroquinolines (DHQs) and quinolones (JohnPhos = (2-biphenyl)di-
tert
-butylphosphine)
Scheme 7.3 Synthesis of substituted quinolines via gold- and copper-catalyzed intramolecular hydroarylation.
Scheme 7.4 Copper-catalyzed KA
2
-hydroarylation for the preparation of 3-spiroheterocyclic 2-oxindoles.
Scheme 7.5 Copper-catalyzed hydroarylation for the synthesis of dihydroquinolines.
Scheme 7.6 Gold-catalyzed regiodivergent hydroarylation of propargylic anilines.
Scheme 7.7 Copper-catalyzed alkyne hydroarylation of
N
-propargylated aminonaphthoquinones and aminoquinoxalines.
Scheme 7.8 Silver-catalyzed nitrogen heterocycle formation using propargylated 2-aminopyridines.
Scheme 7.9 Gold-catalyzed atroposelective intramolecular hydroarylation of internal alkynes with anilines.
Scheme 7.10 Gold-catalyzed cycloisomerization of
N
-aminophenyl propargyl malonates.
Scheme 7.11 Gold-catalyzed cycloisomerization of
N
-propargyl-
N
′-arylhydrazines.
Scheme 7.12 Regioselectivity in the gold-catalyzed intramolecular hydroarylation of iodoalkynes with anilines.
Scheme 7.13 Gold- and silver-catalyzed hydroamination/alkynylation/hydroarylation cascade.
Scheme 7.14 Gold-catalyzed tandem hydroamination/alkynylation/hydroarylation in the synthesis of pyrroloquinolines.
Scheme 7.15 Gold- and indium-catalyzed tandem hydroarylation/Prins reaction in the synthesis of pyranoquinolines.
Scheme 7.16 Gold-catalyzed cycloisomerization of polyalkoxyaryl propargyl ethers.
Scheme 7.17 Effect of AgOTf-additive on efficiency of gold-catalyzed intramolecular hydroarylation of aryl propargyl ether.
Scheme 7.18 Target-oriented gold-catalyzed intramolecular hydroarylation of phenyl propargyl ethers.
Scheme 7.19 Gold-catalyzed intramolecular hydroarylations of aryl propargyl ethers and aryl propiolates.
Scheme 7.20 Gold-catalyzed aryl propargyl ether hydroarylation vs. 1,6-enyne cycloisomerization.
Scheme 7.21 Gold- and silver-catalyzed intramolecular hydroarylation of aryl alkyne tethered propargyl ethers.
Scheme 7.22 Copper-catalyzed intramolecular hydroarylation of alkyne tethered to aryl ether.
Scheme 7.23 Gold-catalyzed cycloisomerization of diynes toward the preparation of bi(2
H
-chromene), bi-dihydroquinoline, and their hybrid derivatives.
Scheme 7.24 Gold-catalyzed intramolecular hydroarylation of iodoalkyne tethered to aryl ether.
Scheme 7.25 Gold-catalyzed cycloisomerization of aryl alkynylphosphonates.
Scheme 7.26 Gold-catalyzed intramolecular cycloisomerization of aryl propiolates for the synthesis of coumarin-containing analogs of serotonin.
Scheme 7.27 Application of gold-catalyzed hydroarylation of alkynes tethered to aryl ethers in the syntheses of berkelic acid tetracyclic core.
Scheme 7.28 Application of gold-catalyzed hydroarylation of alkynes tethered to aryl esters in sensing of Au(III) ions and synthesis of luminogens.
Scheme 7.29 Gold-catalyzed hydroarylation in the synthesis of spirocyclic lactones.
Scheme 7.30 Gold-catalyzed spirocyclization of alkyne-tethered phenols.
Scheme 7.31 Gold-catalyzed intramolecular dearomative spirocyclization of naphthols.
Scheme 7.32 Gold-catalyzed intramolecular cycloisomerization of
o
-alkynylbiaryls.
Scheme 7.33 The application of cyclopropenium-substituted phosphine ligands in gold-catalyzed hydroarylation of
o
-alkynylbiaryls.
Scheme 7.34 Gold- and copper-catalyzed hydroarylation in the synthesis of aryl-substituted phenanthrenes and benzo[
a
]phenanthridines.
Scheme 7.35 Gold-catalyzed intramolecular hydroarylation of
ortho
-alkynylaryl ferrocenes.
Scheme 7.36 The application of gold-catalyzed intramolecular hydroarylation for the synthesis of anthracene derivatives.
Scheme 7.37 Gold-catalyzed hydroarylation of
ortho
-propargylated biaryls in the synthesis of phenanthrenes.
Scheme 7.38 Gold-catalyzed intramolecular hydroarylation in the synthesis of fluoranthenes.
Scheme 7.39 Gold-catalyzed intramolecular hydroarylation of alkynes in the synthesis of dibenzazepine derivatives.
Scheme 7.40 Gold-catalyzed intramolecular hydroarylation of terminal alkynes in the synthesis of dibenzocycloheptatrienes.
Scheme 7.41 Intramolecular hydroarylation of (
o
-arylphenyl)alkynyl halides catalyzed by π-acids. Application of a gold-catalyzed transformation to the synthesis of iodinated picene and dibenzo[
a
,
h
]anthracene derivatives.
Scheme 7.42 Proposed mechanisms of halogen migration during gold-catalyzed hydroarylation of [
o
-(
m
-xylyl)phenyl]alkynyl halides.
Scheme 7.43 Gold-catalyzed cycloisomerization of (
o
-arylphenyl)alkynyl selenides in the synthesis of seleno-substituted phenanthrenes.
Scheme 7.44 Synthesis of benzannulated dihydrofurans via Rh-catalyzed cyclopropanation, Lewis acid-promoted cyclopropane opening, gold-catalyzed hydroarylation sequence.
Scheme 7.45 Gold-catalyzed synthesis of benzonorcaradiene skeleton involving an alkyne hydroarylation.
Scheme 7.46 Gold-catalyzed cyclization of propargylated 1,2-dimethyltryptamine into spirocyclic 2-methyleneindoline.
Scheme 7.47 General mechanism of gold-catalyzed intramolecular hydroarylation of alkynes with indole.
Scheme 7.48 Gold-catalyzed cyclization of tryptamines, bearing terminal alkyne into azepinoindoles and indoloazocines, through spirocyclic indolenine intermediate.
Scheme 7.49 Gold-catalyzed cyclization of internal propargylated tryptamines.
Scheme 7.50 Gold-catalyzed intramolecular hydroarylation of tryptamine-derived propargylamides.
Scheme 7.51 Gold-catalyzed formation of dihydrocarbazoles.
Scheme 7.52 Silver- and gold-catalyzed syntheses of carbazoles.
Scheme 7.59 Silver-catalyzed intramolecular spirocyclization reactions of indole–ynes.
Scheme 7.53 Gold-catalyzed hydroarylation of indole-2-(
N
-propargylcarboxamides).
Scheme 7.54 Copper-catalyzed intramolecular hydroarylation in the synthesis of β-carboline-containing compounds.
Scheme 7.55 Synthesis of carbazoles by gold-catalyzed intramolecular hydroarylation of internal alkynes with indoles.
Scheme 7.56 Gold-catalyzed deacylative hydroarylation of internal alkynes with indoles.
Scheme 7.57 Gold-catalyzed ring expansion and spirocyclization of propargyl-β-tetrahydrocarbolines.
Scheme 7.58 Mechanism of gold-catalyzed intramolecular hydroarylation of propargyl-β-tetrahydrocarbolines.
Scheme 7.60 Gold-catalyzed desilylative spirocyclization.
Scheme 7.61 Gold-catalyzed intramolecular alkyne hydroarylation with 3-aryloxy indoles.
Scheme 7.62 Gold-catalyzed intramolecular hydroarylation/iminium trapping cascade.
Scheme 7.63 Gold-catalyzed synthesis of pyran- and furan-fused indolines via hydroarylation/heteronucleophilic iminium trapping sequence.
Scheme 7.64 Gold-catalyzed intramolecular hydroarylation/iminium sequence for indole-ynamides.
Scheme 7.65 Gold-catalyzed intramolecular hydroamination/hydroarylation cascade for the synthesis of aryl-fused carbazoles.
Scheme 7.66 Application of gold-catalyzed hydroamination/hydroarylation cascade for the preparation of polyaromatic compounds.
Scheme 7.67 Synthesis of dihydronaphthofuran, azepino-, oxepino-, and dihydrobenzoindoles through gold-catalyzed hydroamination/hydroarylation cascade.
Scheme 7.68 Approach to donor–acceptor–donor molecules via gold-catalyzed hydroamination/hydroarylation cascade.
Scheme 7.69 Friedel−Crafts α-amidoalkylation/hydroarylation sequence.
Scheme 7.70 Gold-catalyzed Friedel–Crafts/hydroarylation cascade reaction of indoles with (
Z
)-enynols.
Scheme 7.71 Gold-catalyzed tandem cycloisomerization/Friedel–Crafts/hydroarylation reaction of diyne–enones with indoles.
Scheme 7.72 Gold-catalyzed Michael addition/hydroarylation cascade reaction of indoles with enynones.
Scheme 7.73 Racemic and enantioselective versions of tandem gold-catalyzed Michael addition/hydroarylation reaction of indoles and
o
-alkynylnitrostyrenes.
Scheme 7.74 Gold-catalyzed oxidative cyclocondestation/hydroarylation cascade.
Scheme 7.75 Copper-catalyzed formation of ynamides and following silver-catalyzed hydroarylation.
Scheme 7.76 Gold-catalyzed hydroarylation in C-2-tethered products of Ugi 4-component reaction.
Scheme 7.77 Ugi reaction in the synthesis of the precursors for the gold-catalyzed hydroarylation/amide-iminium cyclization.
Scheme 7.78 Gold-catalyzed hydroarylation in C-3-tethered products of Ugi 4-component reaction.
Scheme 7.79 A post-Ugi divergent intramolecular hydroarylation of internal alkynes tethered at the indole 4-position.
Scheme 7.80 Gold-catalyzed hydroarylation of alkynes with indole-3-carboxamides via 3,2-acylamino shift.
Scheme 7.81 Silver-catalyzed synthesis of tetrahydrocarbazoles.
Scheme 7.82 Gold-catalyzed rearrangement of 1,1-bis(indolyl)-5-alkynes.
Scheme 7.83 Gold-catalyzed alkyne hydroarylation with subsequent heterolytic fragmentation in the synthesis of 3-allenyl indoles.
Scheme 7.84 Gold-catalyzed arylation of alkynes as a key step in the cycloisomerization of 3-propargylic indoles into indenes.
Scheme 7.85 Gold-catalyzed hydroarylation of 2-propargylamide-substituted pyrroles.
Scheme 7.86 Gold-catalyzed cycloisomerization of β-yne-pyrroles.
Scheme 7.87 The application of gold-catalyzed intramolecular hydroarylation to the synthesis of pyrrolo[1,2-
a
]quinolines.
Scheme 7.88 Organocatalytic asymmetric Michael addition, gold-catalyzed intramolecular hydroarylation sequence.
Scheme 7.89 Copper-catalyzed asymmetric Michael addition, gold-catalyzed intramolecular hydroarylation sequence.
Scheme 7.90 Gold-catalyzed alkyne hydroarylation reaction of products of Ugi four-component condensation between 2-formyl
N
-methylpyrrole, propargyl amine, isonitrile and carboxylic acid.
Scheme 7.91 Gold- and platinum-catalyzed hydroarylation reactions of products of Ugi four-component condensation between 2-formyl-pyrrole, 2-alkynoic acid, isonitrile, and primary amine.
Scheme 7.92 Silver- and indium-catalyzed hydroarylation reactions of products of Ugi four-component condensation between 3-formyl-pyrrole, 2-alkynoic acid, isonitrile, and primary amine.
Scheme 7.93 Gold-catalyzed hydroarylation reaction of products of Ugi four-component condensation between 2-(pyrrol-1-yl)-benzaldehyde, 2-alkynoic acid, isonitrile, and benzylic amine.
Scheme 7.94 Normal and abnormal reactivity of furans in intramolecular gold-catalyzed hydroarylation of tethered alkynes.
Scheme 7.95 Gold-catalyzed cycloisomerization of 3-furyl tethered alkynes in the synthesis of seven-membered ring containing polyheterocycles and crassifolone skeleton.
Scheme 7.96 Gold-catalyzed benzannulation of furans.
Scheme 7.97 Application of gold-catalyzed hydroarylation to the preparation of polyaromatic ribbons.
Scheme 7.98 Gold-catalyzed hydroarylation in the synthesis of benzofurans.
Scheme 7.99 Gold-catalyzed cycloisomerization of furan–ynes.
Scheme 7.100 Gold-catalyzed hydroarylation of furans in the synthesis of naphthols and its application in the total synthesis of wailupemycin G.
Scheme 7.101 Gold-catalyzed cycloisomerization of enynyl furans in the synthesis of fulvene derivatives.
Scheme 7.102 Dependence of the outcome of gold-catalyzed cycloisomerization of furan–ynes on the tether length.
Scheme 7.103 Gold-catalyzed cycloisomerization of furans tethered to aryl alkynyl ether leading to the formation of complex tetracylcles.
Scheme 7.104 Gold-catalyzed intramolecular hydroarylation of furan–ynes in the synthesis of trisubstituted alkenes and indenes.
Scheme 7.105 Gold-catalyzed Friedel–Crafts reaction/cycloisomerization cascade in the synthesis of (
Z
)-enones and -enals.
Scheme 7.106 Gold-catalyzed Friedel–Crafts reaction/cycloisomerization cascade in the synthesis of phenanthrene derivatives.
Scheme 7.107 Gold-catalyzed intramolecular hydroarylation of furan–ynes leading to phenols.
Scheme 7.108 Mechanism of platinum- and gold-catalyzed formation of phenols from furan–ynes.
Scheme 7.109 “Oxygen walk” mechanism for the formation of regioisomeric phenols in hydroarylation of furan–ynes.
Scheme 7.110 Gold (III)-catalyzed cycloisomerization of furan–ynes in the preparation of polyarenes and biologically relevant molecules.
Scheme 7.111 Cascade transformations involving gold(III)-catalyzed cycloisomerization of furan–ynes.
Scheme 7.112 Induction of diastereo- and enantioselectivity in gold-catalyzed cycloisomerization of furan–ynes.
Scheme 7.113 Gold-catalyzed cycloisomerization of furan–ynes for the preparation of enantioenriched compounds.
Scheme 7.114 Gold-catalyzed rearrangement of thiophene- and benzothiophene-derived homopropargyl silanols.
Scheme 7.115 Gold-catalyzed alkyne hydroarylation reaction of products of Ugi four-component condensation between 3-formyl-benzothiophene, 2-carboxylic acid, isonitrile, and propargylamine.
Scheme 7.116 Gold- and copper-catalyzed protocols for the intermolecular hydroarylation of aryl alkynes with electron-rich arenes.
Scheme 7.117 Gold-catalyzed intermolecular hydroarylation of electron-poor alkynes with electron-rich arenes.
Scheme 7.118 Gold-catalyzed intermolecular hydroarylation/cycloisomerization of 1,2-bis(2-haloethynyl)benzenes.
Scheme 7.119 Intermolecular double hydroarylation of alkynes with indoles at the terminal alkyne position with the formation of bis-indoles.
Scheme 7.120 Different outcome of the gold-catalyzed intermolecular alkyne hydroarylation with indoles.
Scheme 7.121 Gold- and copper-catalyzed intermolecular hydroarylation of alkynes with pyrroles.
Scheme 7.122 Gold-catalyzed intermolecular hydroarylation of ynamides with 3-substituted indoles.
Scheme 7.123 Gold-catalyzed intermolecular hydroarylation of 1,3-diynes with indoles and pyrroles.
Scheme 7.124 Gold-catalyzed intermolecular hydroarylation/enyne cycloisomerization cascade in the synthesis of NH-carbazoles.
Scheme 7.125 Gold-catalyzed intermolecular hydroarylation/cycloaromatization cascade in the synthesis of indolizines.
Scheme 7.126 Intermolecular double hydroarylation of terminal alkynes with furans.
Scheme 7.127 Intermolecular gold-catalyzed hydroarylation of alkynes with furans in the synthesis of phenols.
Scheme 7.128 Gold-catalyzed intermolecular hydroarylation of alkynes with 1,3-diphenylisobenzofuran.
Scheme 7.129 Gold-catalyzed hydroarylation of ethynyl ethers and 1,3-diynes with 2,5-disubstituted furans.
Scheme 7.130 Intramolecular furan–yne cycloisomerization catalyzed by nanoparticles of gold supported on nanocrystalline CeO
2
.
Scheme 7.131 Intramolecular furan–yne cycloisomerization catalyzed by gold(III) immobilized silica nanoparticles.
Scheme 7.132 Polystyrene-gold(I) (PS = polystyrene) catalyst applied to the furan–yne cycloisomerization.
Scheme 7.133 Cycloisomerization of aryl propargyl ethers catalyzed by gold nanoparticles supported on titanium oxide.
Scheme 7.134 Cycloisomerization of propargylic anilines catalyzed by gold nanoparticles supported on titanium oxide or aluminum oxide.
Scheme 7.135 A post-Ugi intramolecular hydroarylation of internal alkynes tethered to indole 3-position catalyzed by supported gold nanoparticles.
Scheme 7.136 Spirocyclization catalyzed by silica-supported silver nitrate.
Scheme 7.137 Application of the gold-catalyzed hydroarylation of aryl propiolates in the total synthesis of pimpinellin, fraxetin, and purpurasol.
Scheme 7.138 Application of the gold-catalyzed hydroarylation of furan–ynes in the total synthesis of wailupemycin G.
Scheme 7.139 Gold-catalyzed alkyne hydroarylation using indole–yne in the formal synthesis of (±)-strictamine.
Scheme 7.140 The application of gold(I)-catalyzed hydroarylation in propargylated tryptamines in the total synthesis of (−)-lundurines A−C.
Scheme 7.141 Silver-catalyzed hydroarylation of propargylated 2-aminopyridines in the synthesis of saripidem.
Chapter 8: 8
Scheme 8.1 Carbometallation of alkynes and subsequent reaction with electrophiles.
Scheme 8.2 Alkyne hydroarylation and “formal” alkyne hydroarylation via carbometallation/protonation.
Scheme 8.3 Carbopalladation of alkynes and subsequent reaction with hydride.
Scheme 8.4 Rh-catalyzed hydroarylation of alkynes using arylboron reagents.
Scheme 8.5 Deuterium-labeling experiments and proposed mechanism for Rh-catalyzed hydroarylation of alkynes using arylboronic acids.
Scheme 8.6 Rh-catalyzed hydroarylation of aza-heteroaryl-substituted alkynes using arylboronic acids.
Scheme 8.7 Rh-catalyzed hydroarylation of alkynes using arylboronic acids under biphasic conditions.
Scheme 8.8 Rh-catalyzed hydroarylation of propargylic alcohol, propargyl sulfone, and ynamides using arylboronic acids.
o
Scheme 8.29 Synthesis of heterocyclic allylsilanes via Pd-catalyzed reductive Heck cyclization.
Scheme 8.30 Synthesis of medium-ring
N
-heterocycles via Pd-catalyzed reductive Heck cyclization under microwave irradiation conditions.
Scheme 8.31 Synthesis of medium-ring N-heterocycles via Pd-catalyzed reductive Heck cyclization under conventional heating conditions.
Scheme 8.32 Synthesis of butenolides via Pd-catalyzed reductive Heck reaction and subsequent lactonization.
Scheme 8.33 Synthesis of butenolides via alkyne hydroarylation using arylboronic acids and subsequent lactonization.
Scheme 8.34 Synthesis of butenolides, pentenolides, and coumarins via Cu-catalyzed alkyne hydroarylation using arylboronic acids and subsequent lactonization.
Scheme 8.35 Synthesis of coumarin and chromenes via reductive Heck reaction and subsequent cyclization.
Scheme 8.36 Synthesis of benzoxepinones via alkyne hydroarylation and subsequent lactonization.
Scheme 8.37 Synthesis of quinolines via reductive Heck reaction and subsequent cyclization.
Scheme 8.38 Synthesis of diarylquinolines via alkyne hydroarylation using
p
-iodotoluene or arylboron reagents and subsequent cyclization.
Scheme 8.39 Synthesis of 2,4-disubstituted quinolines via Ni-catalyzed reductive Heck reaction of
o
-iodoaniline with alkynones and subsequent cyclization.
Scheme 8.40 Synthesis of 3-aryl-1,2-dihydroquinolines via Rh-catalyzed hydroarylation of propargylamines with arylboronic acids and subsequent Pd-catalyzed intramolecular amidation.
Scheme 8.41 Synthesis of 3-arylindole-2-carboxylates via Cu-catalyzed hydroarylation of (
o
-nitrophenyl)propiolate with arylboronic acids and subsequent Cadogan cyclization.
Scheme 8.42 Synthesis of 4-aryl-1,2-oxaphospholene 2-oxides via Pd-catalyzed hydroarylation of 3-hydroxypropynyl phosphonates with arylboronic acids and subsequent cyclization.
Scheme 8.43 Synthesis of α-tetralones via sequential process involving Rh-catalyzed alkyne hydroarylation and 1,4-Rh shift.
Scheme 8.44 Asymmetric synthesis of 3,3-disubstituted 1-indanones via sequential process involving Rh-catalyzed alkyne hydroarylation and 1,4-Rh shift.
Scheme 8.45 Synthesis of spirocycles via sequential process involving Rh-catalyzed alkyne hydroarylation and 1,4-Rh shift.
Scheme 8.46 Synthesis of conformationally restrained analogs of GR85305 via Pd-catalyzed reductive Heck cyclization.
Scheme 8.47 Synthesis of antirhinoviral agents via Pd-catalyzed reductive Heck reaction.
Scheme 8.48 Synthesis of 2-arylquinolines via Ni-catalyzed reductive Heck type reaction and subsequent cyclization.
Scheme 8.49 Synthesis of analogs of (−)-aphanorphine via Pd-catalyzed reductive Heck cyclization.
Scheme 8.50 Synthesis of natural neoflavones via Cu-catalyzed alkyne hydroarylation using arylboronic acids and subsequent cyclization.
Scheme 8.51 Synthesis of CC-5079 via Cu-catalyzed hydroarylation of propynenitriles using arylboronic acids.
Chapter 9: Transition Metal-Catalyzed Hydroarylation of Allenes
Scheme 9.1 Gold-catalyzed 6-
exo
hydroarylation of 2-allenyl indole
1
.
Scheme 9.2 Proposed mechanism of the gold(I)-catalyzed hydroarylation of 2-allenyl indoles.
Scheme 9.3 Gold-catalyzed 5-
exo
hydroarylation of
N
-allenyl indole
3
as a route to flinderole B and C.
Scheme 9.4 Gold-catalyzed 6-
endo
hydroarylation of
N
-allenyl indoles.
Scheme 9.5 Deuterium distribution in the gold-catalyzed 6-
endo
hydroarylation of 2-deuterio indole
5
-2-
d
1
.
Scheme 9.6 Scope of the gold-catalyzed 5-
endo
hydroarylation of 3-allenyl indoles.
Scheme 9.7 Gold-catalyzed hydroarylation of
7b
in the presence of CD
3
COOD.
Scheme 9.8 Gold-catalyzed intramolecular 7-
exo
hydroarylation of β-lactam-tethered allenyl indoles.
Scheme 9.9 Gold-catalyzed intramolecular hydroarylation of lactam-tethered allenyl indoles.
Scheme 9.10 Gold-catalyzed 6-
exo
hydroarylation of allenes with pyrroles as a route to (−)-rhazinilam.
Scheme 9.11 Gold-catalyzed intramolecular 6-
exo
hydroarylation of allenes with substituted arenes.
Scheme 9.12 Generation and reactivity of mono(gold) and bis(gold) vinyl complexes in the gold-catalyzed hydroarylation of allenes with substituted arenes.
Scheme 9.13 Formation of silver/gold dimetallated vinyl complex
22
from the reaction of
18
with a mixture of gold and silver.
Scheme 9.14 Gold-catalyzed intramolecular 6-
exo
hydroarylation of allenes with furans.
Scheme 9.15 Platinum-catalyzed 6-
exo
hydroarylation of allenes with furans.
Scheme 9.16 Synthesis of chromanes via the gold-catalyzed intramolecular 6-
exo
hydroarylation of aryl allenyl ethers.
Scheme 9.17 Gold-catalyzed intramolecular 6-
endo
hydroarylation of an allene with benzene derivatives.
Scheme 9.18 Platinum-catalyzed 6-
endo
hydroarylation of 2-benzyl-2,3-butadienoates.
Scheme 9.19 Gold(I)-catalyzed 6-
endo
intramolecular hydroarylation of aryl allenes containing a 1,3-disubstituted allene moiety.
Scheme 9.20 Gold(I)-catalyzed diastereoselective 6-
endo
hydroarylation of enantiomerically enriched 1,3-disubstituted allenes.
Scheme 9.21 Gold-catalyzed intramolecular hydroarylation of
N
-allenyl anilines.
Scheme 9.22 Gold-catalyzed intramolecular 7-
exo
hydroarylation of an allene with a pyrrole (a) and the 5-
endo
hydroarylation of an allene with a phenyl group (b).
Scheme 9.23 Gold-catalyzed 9-
endo
hydroarylation of (aryl)allene-tethered 2-azetidinones.
Scheme 9.24 Gold-catalyzed intermolecular hydroarylation of allenes with indoles.
Scheme 9.25 Platinum(IV)-catalyzed tandem hydroarylation/hydroalkoxylation of indoles with allenyl alcohols.
Scheme 9.26 Platinum-catalyzed intermolecular bisindolylation of allenes to form 1,1-bis (indolyl) alkanes.
Scheme 9.27 Gold(III)-catalyzed tandem cyclization/hydroarylation of allenyl ketones.
Scheme 9.28 Platinum(II)-catalyzed and Platinum(II)-mediated intermolecular hydroarylation of substituted arenes with 3-methyl-1,2-butadiene.
Scheme 9.29 Gold-catalyzed intermolecular hydroarylation of allenes with electron-rich arenes.
Scheme 9.30 Pd(II)/Brønsted acid-catalyzed intermolecular hydroarylation of allenoates with alkoxyl benzenes.
Scheme 9.31 Gold(I)-catalyzed hydroarylation of 1-phenyl-1,2-propadiene with substituted arenes.
Scheme 9.32 Gold-catalyzed enantioselective intramolecular 6-
exo
hydroarylation of 2-allenyl indoles.
Scheme 9.33 Gold-catalyzed enantioselective intermolecular hydroarylation of 1,3-diaryl allenes with indoles.