Cleavage of Carbon-Carbon Single Bonds by Transition Metals E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 309

Veröffentlichungsjahr: 2015

Beschreibung

Edited by leading experts and pioneers in the field, this is the first up-to-date book on this hot topic. The authors provide synthetic chemists with different methods to activate carbon-carbon sigma bonds in organic molecules promoted by transition metal complexes. They explain the basic principles and strategies for carbon-carbon bond cleavage and highlight recently developed synthetic protocols based on this methodology. In so doing, they cover cleavage of C-C bonds in strained molecules, reactions involving elimination of carbon dioxide and ketones, reactions via retroallylation, and cleavage of C-C bonds of ketones and nitriles. The result is an excellent information source for researchers in academia and industry working in the field of synthetic organic chemistry, while equally serving as supplementary reading for advanced courses in organometallic chemistry and catalysis.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Fundamental Reactions to Cleave Carbon–Carbon σ-Bonds with Transition Metal Complexes

1.1 Introduction

1.2 Oxidative Addition

1.3 β-Carbon Elimination

1.4 Retroallylation

1.5 Migratory Deinsertion of a Carbonyl Group

1.6 Decarboxylation

1.7 Retro-oxidative Cyclization

1.8 1,2-Migration

1.9 Cleavage of C–C Multiple Bonds

1.10 Summary

References

Chapter 2: Reactions of Three-Membered Ring Compounds

2.1 Introduction

2.2 Cyclopropanes

2.3 Bicyclo[1.1.0]butanes

2.4 Bicyclo[2.1.0]pentanes

2.5 Quadricyclanes and Related Compounds

2.6 Spiropentanes

2.7 Cyclopropanols

2.8 Vinylcyclopropanes

2.9 Methylenecyclopropanes

2.10 Alkynylcyclopropanes

2.11 Cyclopropyl Ketones and Imines

2.12 Cyclopropenes

2.13 Benzocyclopropenes

2.14 Cyclopropenones

2.15 Conclusion

References

Chapter 3: Reactions of Four-Membered Ring Compounds

3.1 Introduction

3.2 Cubane Derivatives

3.3 Biphenylenes

3.4 Vinylcyclobutane and Methylenecyclobutane Derivatives

3.5 Cyclobutanol and Cyclobutanone Derivatives

3.6 Cyclobutenones and Cyclobutenediones

3.7 Conclusion

References

Chapter 4: Reactions Involving Elimination of CO2 and Ketones

4.1 Introduction

4.2 Reactions of Benzoic Acids

4.3 Reactions of Heteroarenecarboxylic Acids

4.4 Reactions of Acrylic Acids

4.5 Reactions of Propiolic Acids

4.6 Reactions of α-Keto Carboxylic Acids

4.7 Reactions of Alkanoic Acids

4.8 Reactions of Tertiary Alcohols

4.9 Summary and Conclusions

References

Chapter 5: Retro-allylation and Deallylation

5.1 Introduction

5.2 Retro-allylation

5.3 Deallylation

5.4 Summary and Conclusions

References

Chapter 6: Reactions via Cleavage of Carbon–Carbon Bonds of Ketones and Nitriles

6.1 Introduction

6.2 Catalytic Reactions of Ketones via C−C Bond Cleavage

6.3 Catalytic Reactions of Nitriles via C−C Bond Cleavage

6.4 Summary and Outlook

References

Chapter 7: Miscellaneous

7.1 Introduction

7.2 Cleavage of C−C Single Bonds

7.3 Cleavage of C=C Double Bonds

7.4 Cleavage of C−C Bonds of Aromatics

7.5 Cleavage of C≡C Triple Bonds

7.6 Summary

References

Chapter 8: Total Syntheses of Natural Products and Biologically Active Compounds by Transition-Metal-Catalyzed C–C Cleavage

8.1 Introduction

8.2 Synthesis of (±)-Nanaomycin A through Alkyne Insertion into a C–C Bond of Benzocyclobutenedione

8.3 Enantioselective Synthesis of (−)-Pseudolaric Acid B via an Intramolecular [5+2] Cycloaddition Reaction of a Vinylcyclopropane with an Alkyne

8.4 Enantioselective Synthesis of (−)-Esermethole via Asymmetric Alkene Insertion into a C–C Bond of Aryl Cyanides

8.5 Enantioselective Synthesis of Benzobicyclo[2.2.2]octenones via Asymmetric Alkene Insertion into a C–C Bond of Cyclobutanones

8.6 Synthesis of the Proposed Structure of Cycloinumakiol through Site-Selective Insertion of Alkenes into a C–C Bond of Benzocyclobutenones

8.7 Enantioselective Synthesis of (−)-(R)-Herbertenol through Asymmetric C–C Cleavage

8.8 Enantioselective Synthesis of (+)-Laurene via Ring-Expansion of 1-Vinylcyclobutanol

8.9 Synthesis of (±)-Cuparenone through Skeletal Reorganization of Spiropentanes

8.10 Total Synthesis of (−)-Cyanthiwigin F by Decarboxylative Asymmetric Allylation

8.11 Total Syntheses via Hydrogenolysis of Cyclopropanes

8.12 Total Syntheses via Decarbonylation

8.13 Summary and Conclusions

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Begin Reading

List of Illustrations

Chapter 1: Fundamental Reactions to Cleave Carbon–Carbon σ-Bonds with Transition Metal Complexes

Scheme 1.1

Figure 1.1 Orbital interactions of a metal with C=C, C−H, C−C bonds.

Figure 1.2 Orbital interactions of a metal with a C−C bond of cyclopropane.

Scheme 1.2

Scheme 1.3

Figure 1.3 A rhodium complex with an agostic interaction with a C−C bond.

Scheme 1.4

Scheme 1.5

Scheme 1.6

Scheme 1.7

Figure 1.4 Schematic model of orbital interaction in a rhodium complex with a C−C−H η

3

-agostic interaction.

Scheme 1.8

Scheme 1.9

Scheme 1.10

Scheme 1.11

Scheme 1.12

Scheme 1.13

Scheme 1.14

Scheme 1.15

Scheme 1.16

Scheme 1.17

Scheme 1.18

Scheme 1.19

Scheme 1.20

Scheme 1.21

Scheme 1.22

Scheme 1.23

Scheme 1.24

Scheme 1.25

Scheme 1.26

Scheme 1.27

Scheme 1.28

Scheme 1.29

Scheme 1.30

Scheme 1.31

Scheme 1.32

Scheme 1.33

Scheme 1.34

Scheme 1.35

Scheme 1.36

Scheme 1.37

Figure 1.5 Conformations of alkylmetallocenes.

Scheme 1.38

Scheme 1.39

Scheme 1.40

Scheme 1.41

Scheme 1.42

Scheme 1.43

Scheme 1.44

Scheme 1.45

Scheme 1.46

Scheme 1.47

Scheme 1.48

Scheme 1.49

Scheme 1.50

Scheme 1.51

Scheme 1.52

Scheme 1.53

Scheme 1.54

Scheme 1.55

Scheme 1.56

Scheme 1.57

Scheme 1.58

Scheme 1.59

Scheme 1.60

Scheme 1.61

Scheme 1.62

Scheme 1.63

Scheme 1.64

Scheme 1.65

Scheme 1.66

Scheme 1.67

Scheme 1.68

Scheme 1.69

Scheme 1.70

Scheme 1.71

Chapter 2: Reactions of Three-Membered Ring Compounds

Scheme 2.1 Hydrogenolysis of cyclopropanes. (TBS:

tert

-butyldimethylsilyl.)

Scheme 2.2 Ring opening of (phosphino)oxy-substituted cyclopropane

1

.

Scheme 2.3 Ring opening of siloxy- and acetoxy-substituted cyclopropanes.

Scheme 2.4 Regioselective ring opening of vinylcyclopropanes by hydrogenation.

Scheme 2.5 Pt(II)-catalyzed rearrangement of siloxycyclopropane

2

.

Scheme 2.6 Rearrangement of alkoxy- and hydroxy-substituted cyclopropanes

4

.

Scheme 2.7 Ring opening of 1,2-cyclopropanated sugar

7

with alcohol

8

. (Bn: benzyl.)

Scheme 2.8 Pd(II)-catalyzed rearrangement of bicyclo[6.1.0]non-4-ene to cyclonona-1,5-diene.

Scheme 2.9 Pd(II)-catalyzed oxidative transformation of arylcyclopropane.

Scheme 2.10 Synthesis of benzochromene via cyclopropane ring opening. (Cy: cyclohexyl, Piv: pivaloyl.)

Scheme 2.11 Synthesis of nitrogen heterocycle via cyclopropane ring opening. (µw: microwave)

Scheme 2.12 V-catalyzed ring-opening isomerization of cyclopropanemethanol

11

.

Scheme 2.13 Tandem ring-opening isomerization/intramolecular hydroalkoxylation.

Scheme 2.14 Rh(I)-catalyzed carbonylative [3+2+1] annulation of cyclopropane–ynes.

Scheme 2.15 Rearrangements of bicycle[1.1.0]butanes.

Scheme 2.16 Ag(I)-catalyzed rearrangement of bicyclobutane

14

containing butadiene–Fe(CO)

3

moiety.

Scheme 2.17 Rearrangement of tricycloheptane in methanol.

Scheme 2.18 Hydrogenation of bicyclobutanes.

Scheme 2.19 Partial hydrogenation of steroidal bicyclobutane.

Scheme 2.20 Ni(0)-catalyzed reaction of bicyclobutane and methyl acrylate.

Scheme 2.21 Rh(I)-catalyzed intramolecular reaction of bicyclobutane–ene. (Ts:

p

-toluenesulfonyl.)

Scheme 2.22 Rh(I)-catalyzed reaction of

endo

-5-methylbicyclo[2.1.0]pentane.

Scheme 2.23 Ni(0)-catalyzed annulation between bicyclopentane and electron-deficient alkenes.

Scheme 2.24 Rh(I)-catalyzed rearrangement of prismane to Dewar benzene.

Scheme 2.25 Rh(I)-catalyzed rearrangement of quadricyclane 25 to norbornadiene 24.

Scheme 2.26 Ni(0)-catalyzed [3+2] annulation of quadricyclane 25 with methyl acrylate.

Scheme 2.27 Conversion of

exo

-homonorbornadiene 27 to tetracyclooctane 28.

Scheme 2.28 Reaction of

exo

-homonorbornadiene

27

in the presence of RhCl(PPh

3

)

3

.

Scheme 2.29 Rh(I)-catalyzed carbonylation of spiropentane

31

. (DPPP: 1,3-bis(diphenylphosphino)propane.)

Scheme 2.30 Tandem Pauson–Khand reaction/spiropentane carbonylation.

Scheme 2.31 Pd(II)-catalyzed oxidative ring opening of cyclopropanols. (TIPS: triisopropylsilyl, dba: dibenzylideneacetone, MS4Å: molecular sieves 4 Å.)

Scheme 2.32 Ir(III)-catalyzed ring opening of cyclopropanols.

Scheme 2.33 Hydrogenolysis of bicyclic cyclopropanol

35

over Pd/C. (THF: tetrahydrofuran.)

Scheme 2.34 Pd(II)-catalyzed rearrangement of 2,2-disubstituted 1-aryl-1-siloxycyclopropane

37

. (TBAF: tetra-

n

-butylammonium fluoride, DMAc:

N

,

N

-dimethylacetamide.)

Scheme 2.35 Cross-coupling of cyclohexanone-derived cyclopropanol

39

with iodobenzene.

Scheme 2.36 Intramolecular cross-coupling yielding spirocyclic product

41

.

Scheme 2.37 Cross-coupling of cyclopropanol

42

and acyl chlorides.

Scheme 2.38 Rearrangement of 1-(1-alkynyl)cyclopropanol to 2-cyclopentenone. (DME: 1,2-dimethoxyethane.)

Scheme 2.39 Intermolecular [5+2] annulation of VCPs.

Scheme 2.40 Pd-catalyzed seven-membered ring formation of VCP–yne

45

.

Scheme 2.41 [5+1] Annulation of VCPs and CO. (DCE: 1,2-dichloroethane.)

Scheme 2.42 Rh(I)-catalyzed carbonylative [5+1] annulation of

in situ

generated allenylcyclopropane

51

.

Scheme 2.43 Carbonylative [7+1] annulation of dienylcyclopropanes.

Scheme 2.44 Rh(I)-catalyzed successive ring opening of bicyclopropyl

54

.

Scheme 2.45 Rh(I)-catalyzed carbonylation of bicyclopropyl

56

.

Scheme 2.46 Rh(I)-catalyzed [5+2+1] annulation of VCPs and CO.

Scheme 2.47 Intermolecular [5+2+1] annulation and subsequent transannular closure.

Scheme 2.48 Four-component [5+2+1+1] annulation.

Scheme 2.49 Rh(I)-catalyzed intramolecular [3+2] annulation of 1-alkynyl-1-vinylcyclopropanes.

Scheme 2.50 Carbonylative [3+2+1] annulation.

Scheme 2.51 Rh(I)-catalyzed [3+2] annulation of VCP

63

having an alkenyl chain.

Scheme 2.52 Intramolecular cyclopropane–alkene [3+2] annulation.

Scheme 2.53 Rh(I)-catalyzed tandem 1,3-acyloxy migration/cycloisomerization.

Scheme 2.54 Ni(0)-catalyzed coupling of VCP–alkyne

67

with allyl chloride.

Scheme 2.55 Pd-catalyzed diastereo- and enantioselective [3+2] annulation of VCP.

Scheme 2.56 Pd-catalyzed [3+2] annulation of VCP

69a

with aldehydes

68

. (bphen: bathophenanthroline.)

Scheme 2.57 [3+2] annulation of VCP

69a

with imines

71

.

Scheme 2.58 Ni(0)-catalyzed rearrangement of 1-acyl-2-vinylcyclopropane

73

.

Scheme 2.59 Ir-catalyzed coupling of VCP

69b

and alcohols.

Figure 2.1 Two cleavage modes of MCP C−C bond

Scheme 2.60 Pd-catalyzed addition of amide and terminal alkyne to MCPs.

Scheme 2.61 Ring-opening isomerization of 3-hydroxymethyl MCP

88

.

Scheme 2.62 Arylative ring opening of 3-hydroxymethyl MCP

88

.

Scheme 2.63 Rh-catalyzed tandem C-H bond activation/cycloisomerization of MCP (1).

Scheme 2.64 Rh-catalyzed tandem C-H bond activation/cycloisomerization of MCP (2).

Scheme 2.65 Mechanism of Pd-catalyzed [3+2] annulation of MCP–yne.

Scheme 2.66 Mechanism of Ni-catalyzed [3+2+2] annulation of MCP and alkynes.

Scheme 2.67 Pd-catalyzed cycloisomerization of methylenecyclopropyl ketone

101

.

Scheme 2.68 Re-catalyzed reaction of vinylidenecyclopropane

105

.

Scheme 2.69 Ni-catalyzed [3+3] homodimerization of MCP

106

.

Scheme 2.70 Ni-catalyzed [3+2+2] annulation of bicyclopropylidene and terminal alkyne

108

.

Scheme 2.71 Co-catalyzed carbonylation of MCP

110

.

Scheme 2.72 Pd-catalyzed [3+2] annulation of MCP and CO

2

. (DMSO: dimethylsulfoxide.)

Scheme 2.73 Ni-catalyzed [3+1+1] annulation of carbene complex

113

and MCP

85

. (DMF:

N

,

N

-dimethylformamide.)

Scheme 2.74 Ni-catalyzed [4+1] annulation of enone

115

and MCP

83

.

Scheme 2.75 Ni-catalyzed decarbonylative annulation of benzothiophenedione

117

and MCP

83

. (MAD: methylaluminum bis(2,6-di-

tert

-butyl-4-methylphenoxide)

Scheme 2.76 Mechanism of Ni-catalyzed [4+1] annulation reactions of MCPs.

Scheme 2.77 Ni-catalyzed [3+2] annulation of methyleneaziridine

119

and diyne.

Scheme 2.78 Pd-catalyzed arylation of 1-alkynylcyclopropanol

121

.

Scheme 2.79 Pd-catalyzed ring-opening hydrosilylation of cyclopropyl ketones.

Scheme 2.80 Ni-catalyzed borylation of cyclopropyl ketones.

Scheme 2.81 Ni-catalyzed dimerization of cyclopropyl ketone

124

.

Scheme 2.82 Cross [3+2] annulation of cyclopropyl ketones.

Scheme 2.83 [3+2] Annulation of cyclopropyl ketones with alkynes.

Scheme 2.84 Carbonylative [5+1] annulation of cyclopropyl imine

126

.

Scheme 2.85 Rh(I)-catalyzed [5+2] annulation of cyclopropyl imine and alkyne.

Scheme 2.86 Rh(I)-catalyzed carbonylation of 1-(1-alkynyl)cyclopropyl ketones.

Scheme 2.87 Formation of transition metal vinyl carbene complexes from cyclopropene.

Scheme 2.88 Rh-catalyzed ring-opening isomerization of 1-benzoylcyclopropene

131

.

Scheme 2.89 Rh(II)-catalyzed rearrangement of 1,2,3-triphenylcyclopropene.

Scheme 2.90 Tandem furan formation/dehydrogenative Heck alkenylation of cyclopropene.

Scheme 2.91 Rearrangement of pyridylcyclopropene

134

.

Scheme 2.92 Mo-catalyzed reaction of triphenylcyclopropene and CO.

Scheme 2.93 Rh(I)-catalyzed [5+2] annulation of 3-benzoylcyclopropene

138

with 1-hexyne.

Scheme 2.94 Rh(I)-catalyzed carbonylation of cyclopropenyl ester

141a

and ketone

141b

.

Scheme 2.95 Carbonylation of alkenylcyclopropene

143

.

Scheme 2.96 Ni-catalyzed [3+2] annulation of cyclopropene and alkyne.

Scheme 2.97 [3+2] Annulation between cyclopropenone acetals and alkyne

130

.

Scheme 2.98 Rh(I)-catalyzed intramolecular cyclopropene–alkyne [3+2] annulation.

Scheme 2.99 Rh(I)-catalyzed carbonylative annulation of cyclopropene–ynes.

Scheme 2.100 [3+2+1] Annulation of cyclopropene–enes.

Scheme 2.101 Rh(II)-catalyzed intramolecular cyclopropanation of cyclopropene–enes.

Scheme 2.102 Fe-catalyzed ring-opening carboalumination of cyclopropenes.

Scheme 2.103 Ag(I)-catalyzed dimerization of benzocyclopropenes.

Scheme 2.104 Ag(I)-catalyzed ring opening of benzocyclopropenes with ethanol.

Scheme 2.105 [3+2] Annulation of benzocyclopropene and aldehyde.

Scheme 2.106 Benzocyclopropene–imine [3+2] annulation.

Scheme 2.107 Ni(0)-catalyzed dimerization of cyclopropenones.

Scheme 2.108 Cu-catalyzed dimerization of cyclopropenones.

Scheme 2.109 Rh(I)-catalyzed [3+2] annulation of cyclopropenone and alkynes.

Scheme 2.110 Ni-catalyzed cyclopropenone–ketene [3+2] annulation.

Scheme 2.111 Ru-catalyzed cyclocarbonylation of cyclopropenones.

Scheme 2.112 Rh-catalyzed reaction of cyclopropenone with Me

3

SiCN.

Scheme 2.113 Pd-catalyzed ring-opening alkynylation of cyclopropenone with terminal alkynes.

Chapter 3: Reactions of Four-Membered Ring Compounds

Scheme 3.1 Rh(I)-catalyzed rearrangement of cubane.

Scheme 3.2 Ag(I)-catalyzed rearrangement of 1,4-disubstituted cubanes.

Scheme 3.3 Rearrangement of homo- and bishomocubanes.

Scheme 3.4 Formation of metallafluorene

1

by oxidative addition of the biphenylene C–C bond.

Scheme 3.5 Rh(I)-catalyzed carbonylation of allenyl- and vinylcyclobutanes. (TBS:

tert

-butyldimethylsilyl.)

Scheme 3.6 Rh(I)-catalyzed intramolecular [6+2] annulation. (Tf: trifluoromethanesulfonyl, Ts:

p

-toluenesulfonyl.)

Scheme 3.7 Ni(0)-catalyzed silaborative C–C bond cleavage of vinylcyclobutane

21

. (acac: acetylacetanato, DIBAH: diisobutylaluminum hydride, pin: pinacolato.)

Scheme 3.8 Rh(I)-catalyzed spiroannulation of methylenecyclobutane

23

. (cod: cycloocta-1,5-diene.)

Scheme 3.9 Rh(I)-catalyzed intramolecular hydroacylation of methylenecyclobutane derivatives

26

.

Scheme 3.10 Pd(II)-catalyzed oxidative ring opening of

tert

-cyclobutanol

27

. (MS3Å: molecular sieves 3Å.)

Scheme 3.11 Pd(II)-catalyzed ring contraction of 1,3,3-trisubstituted cyclobutanol

29

.

Scheme 3.12 Ring opening and subsequent intramolecular cyclization of 1-arylcyclobutanol

31

.

Scheme 3.13 Pd(0)-catalyzed asymmetric arylation of

tert

-cyclobutanol

33

. (Ac: acetyl.)

Scheme 3.14 Pd-catalyzed intramolecular arylative ring opening of cyclobutanols.

Scheme 3.15 Pd-catalyzed reaction of 3-(2-hydroxyphenyl)cyclobutanone

35

with PhBr. (dba: dibenzylideneacetone.)

Scheme 3.16 Pd-catalyzed reaction of 2-(2-hydroxyphenyl)cyclobutanones with aryl halides.

Scheme 3.17 Pd-catalyzed arylative ring opening of benzocyclobutenol

37

. (DavePhos: 2-dicyclohexylphosphino-2'-(

N

,

N

-dimethylamino)biphenyl.)

Scheme 3.18 Asymmetric intramolecular addition/ring opening reaction of 3-(2-borylphenyl)cyclobutanones. (SEGPHOS: 5,5'-bis(dipheylphosphino)-4,4'-bi-1,3-benzodioxole.)

Scheme 3.19 Rh(I)-catalyzed arylation of 2-(2-alkynylphenyl)cyclobutanone

39

.

Scheme 3.20 Ring opening of cyclobutanones with alcohols and amines. (H8-BINAP: 2,2'-bis(diphenylphosphino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl, Bn: benzyl.)

Scheme 3.21 Rh(I)-catalyzed intramolecular reaction of phenol-substituted cyclobutanone

42

.

Scheme 3.22 Reaction of 3,3-disubstituted cyclobutanones and electron-deficient alkenes. (Tol-BINAP: 2,2'-bis(di-

p

-tolylphosphino)-1,1'-binaphthyl.)

Scheme 3.23 Rh(I)-catalyzed asymmetric ring opening of cyclobutanol. (DTBM-SEGPHOS: 5,5'-bis[bis(3,5-di-

tert

-butyl-4-methoxyphenyl)phosphino]-4,4'-bi-1,3-benzodioxole.)

Scheme 3.24 Asymmetric ring-opening reorganization of cyclobutanol

42

. (DIFLUORPHOS: 5,5'-bis(diphenylphosphino)-2,2,2',2',-tetrafluoro-4,4'-bi-1,3-benzodioxole.)

Scheme 3.25 Rh(I)-catalyzed ring opening of 3-(2-silylphenyl)cyclobutanol

44

.

Scheme 3.26 Rh(I)-catalyzed ring opening of 3-(2-silylphenyl)cyclobutanol

44

involving double C–Si bond cleavage.

Scheme 3.27 Rh(I)-catalyzed reaction of 1-(2-bromophenyl)cyclobutanol derivatives

47

.

Scheme 3.28 Rh(I)-catalyzed asymmetric ring-opening reorganization of 1-allenylcyclobutanol

49

. (DTBM-MeO-BIPHEP: 2,2'-bis[bis(3,5-di-

tert

-butyl-4-methoxyphenyl)phosphino]-6,6'-dimethoxy-1,1'-biphenyl.)

Scheme 3.29 Asymmetric isomerization of 1-alkenylcyclobutanol

51

.

Scheme 3.30 Rh(I)-catalyzed ring opening annulation of benzocyclobutenol

53

.

Scheme 3.31 Ring opening annulation of cyclobutenol

55

.

Scheme 3.32 Ni(0)-catalyzed [4+2] annulation of cyclobutanone

58

and alkyne.

Scheme 3.33 [4+2] Annulation of azetidinones

61

and alkyne.

Scheme 3.34 Ni(0)-catalyzed intramolecular [4+2] annulation of 3-(2-alkenylphenyl)cyclobutanones.

Scheme 3.35 Asymmetric [4+2] annulation.

Scheme 3.36 Ni(0)-catalyzed [4+2+2] annulation of cyclobutanone

58

with diyne

62

.

Scheme 3.37 Pd(0)-catalyzed ring opening of cyclobutanone

O

-benzoyloxime

65

.

Scheme 3.38 Pd(0)-catalyzed ring contraction of cyclobutanone

O

-benzoyloxime

66

.

Scheme 3.39

Scheme 3.40 Rh(I)-catalyzed decarbonylation of 3-monosubstituted cyclobutanone.

Scheme 3.41 Intramolecular competitive decarbonylation.

Scheme 3.42 Rhodium(I)-catalyzed hydrogenolysis of cyclobutanone

73

.

Scheme 3.43 Rh(I)-catalyzed rearrangement of spirocyclic cyclobutanone

75

.

Scheme 3.44 Reaction of 2-(phenoxymethyl)cyclobutanone

77

.

Scheme 3.45 Rh(I)-catalyzed intramolecular alkene insertion of 3-(2-vinylphenyl)cyclobutanone

81

. (BHT: 3,5-di-

tert

-butyl-4-hydroxytoluene.)

Scheme 3.46 Rh(I)-catalyzed intramolecular alkene insertion of 2-(2-vinylphenyl)cyclobutanone

83

.

Scheme 3.47

Scheme 3.48 Pd(0)-catalyzed intramolecular C–C/Si-Si metathesis of

87

.

Scheme 3.49 Formation of metallacycles or η

4

-vinylketene complexes from cyclobutenones.

Scheme 3.50 Ni(0)-catalyzed alkyne insertion into cyclobutenone.

Scheme 3.51 Rh(I)-catalyzed reaction of cyclobutenone with electron-deficient alkenes.

Scheme 3.52 Rh(I)-catalyzed [4–1+2] and [4+2] annulations of cyclobutenone

89

.

Scheme 3.53 Rh(I)-catalyzed ring-expanding rearrangement of cyclobutenones

93

.

Scheme 3.54 Ru-catalyzed annulations of cyclobutenediones

95

.

Scheme 3.55 Rh(I)-catalyzed intramolecular decarbonylative annulation of cyclobutenediones.

Chapter 4: Reactions Involving Elimination of CO2 and Ketones

Scheme 4.1

Scheme 4.2

Scheme 4.3

Scheme 4.4

Scheme 4.5

Scheme 4.6

Scheme 4.7

Scheme 4.8

Scheme 4.9

Scheme 4.10

Scheme 4.11

Scheme 4.12

Scheme 4.13

Scheme 4.14

Scheme 4.15

Scheme 4.16

Scheme 4.17

Scheme 4.18

Scheme 4.19

Scheme 4.20

Scheme 4.21

Scheme 4.22

Scheme 4.23

Scheme 4.24

Scheme 4.25

Scheme 4.26

Scheme 4.27

Scheme 4.28

Scheme 4.29

Scheme 4.30

Scheme 4.31

Scheme 4.32

Scheme 4.33

Scheme 4.34

Scheme 4.35

Scheme 4.36

Scheme 4.37

Scheme 4.38

Scheme 4.39

Scheme 4.40

Scheme 4.41

Scheme 4.42

Scheme 4.43

Scheme 4.44

Scheme 4.45

Scheme 4.46

Scheme 4.47

Scheme 4.48

Scheme 4.49

Scheme 4.50

Scheme 4.51

Scheme 4.52

Scheme 4.53

Scheme 4.54

Scheme 4.55

Scheme 4.56

Scheme 4.57

Scheme 4.58

Scheme 4.59

Scheme 4.60

Scheme 4.61

Scheme 4.62

Scheme 4.63

Scheme 4.64

Scheme 4.65

Scheme 4.66

Scheme 4.67

Scheme 4.68

Scheme 4.69

Scheme 4.70

Scheme 4.71

Scheme 4.72

Scheme 4.73

Scheme 4.74

Scheme 4.75

Scheme 4.76

Scheme 4.77

Scheme 4.78

Scheme 4.79

Scheme 4.80

Scheme 4.81

Scheme 4.82

Scheme 4.83

Scheme 4.84

Scheme 4.85

Scheme 4.86

Scheme 4.87

Scheme 4.88

Scheme 4.89

Scheme 4.90

Scheme 4.91

Scheme 4.92

Scheme 4.93

Scheme 4.94

Scheme 4.95

Scheme 4.96

Scheme 4.97

Scheme 4.98

Scheme 4.99

Scheme 4.100

Scheme 4.101

Scheme 4.102

Scheme 4.103

Scheme 4.104

Scheme 4.105

Chapter 5: Retro-allylation and Deallylation

Scheme 5.1

Scheme 5.2

Scheme 5.3

Scheme 5.4

Scheme 5.5

Scheme 5.6

Scheme 5.7

Scheme 5.8

Scheme 5.9

Scheme 5.10

Scheme 5.11

Scheme 5.12

Scheme 5.13

Scheme 5.14

Scheme 5.15

Scheme 5.16

Scheme 5.17

Scheme 5.18

Scheme 5.19

Scheme 5.20

Scheme 5.21

Scheme 5.22

Scheme 5.23

Scheme 5.24

Scheme 5.25

Scheme 5.26

Scheme 5.27

Scheme 5.28

Scheme 5.29

Scheme 5.30

Scheme 5.31

Scheme 5.32

Scheme 5.33

Scheme 5.34

Scheme 5.35

Scheme 5.36

Scheme 5.37

Scheme 5.38

Scheme 5.39

Scheme 5.40

Scheme 5.41

Scheme 5.42

Scheme 5.43

Scheme 5.44

Scheme 5.45

Scheme 5.46

Scheme 5.47

Scheme 5.48

Scheme 5.49

Scheme 5.50

Scheme 5.51

Scheme 5.52

Scheme 5.53

Scheme 5.54

Scheme 5.55

Scheme 5.56

Chapter 6: Reactions via Cleavage of Carbon–Carbon Bonds of Ketones and Nitriles

Scheme 6.1 Insertion of metal fragment into non-polar and polar C−C bonds.

Scheme 6.2 Covalently bound intermediates in C−C bond activation.

Scheme 6.3 Rhodium-catalyzed C−C=O bond activation of 8-acylquinolines.

Scheme 6.4 Intramolecular carboacylation.

Scheme 6.5 Hydroarylation versus carboacylation.

Scheme 6.6 Directed arylation via C−C=O bond cleavage.

Scheme 6.7 2-Aminopicoline as a temporary directing group.

Scheme 6.8 Rhodium-catalyzed ring contraction via C−C=O bond cleavage.

Scheme 6.9 Formal alkyne insertion into a C−C=O bond.

Scheme 6.10 Catalytic conversion of 1,3-diketone to 1,2-diketone.

Scheme 6.11 DuPont's adiponitrile process.

Scheme 6.12 Formal alkyne insertion into acyl cyanide.

Scheme 6.13 Possible catalytic cycle for cross-coupling triggered by oxidative addition of a C−CN bond.

Scheme 6.14 Carbocyanation reaction.

Scheme 6.15 Alkynylcyanation reaction.

Scheme 6.17 Carbocyanation using alkyl cyanides.

Scheme 6.16 Catalytic asymmetric carbocyanation of intramolecular alkene.

Scheme 6.18 Silicon-assisted mechanism for C−CN bond cleavage.

Scheme 6.19 Iron-catalyzed cleavage of a C−CN bond.

Scheme 6.20 Interception of arylrhodium intermediate generated by silicon-assisted C−CN bond cleavage.

Scheme 6.21 Cross-coupling of aryl cyanides with aryl chlorides.

Scheme 6.22 Mizoroki–Heck type reaction using nitriles.

Scheme 6.23 Rhodium-catalyzed borylation of C−CN bonds.

Scheme 6.24 Acetonitrile as a cyano source in catalytic cyanation of aryl bromides.

Scheme 6.25 Iridium-catalyzed cleavage of C

α

-C

β

bond in nitriles.

Chapter 7: Miscellaneous

Scheme 7.1

Scheme 7.2

Scheme 7.3

Scheme 7.4

Scheme 7.5

Scheme 7.6

Scheme 7.7

Scheme 7.8

Scheme 7.9

Scheme 7.10

Scheme 7.11

Scheme 7.12

Scheme 7.13

Scheme 7.14

Scheme 7.15

Scheme 7.16

Scheme 7.17

Scheme 7.18

Scheme 7.19

Scheme 7.20

Scheme 7.21

Scheme 7.22

Scheme 7.23

Scheme 7.24

Scheme 7.25

Scheme 7.26

Scheme 7.27

Scheme 7.28

Scheme 7.29

Scheme 7.30

Scheme 7.31

Scheme 7.32

Scheme 7.33

Scheme 7.34

Scheme 7.35

Scheme 7.36

Scheme 7.37

Scheme 7.38

Scheme 7.39

Scheme 7.40

Scheme 7.41

Scheme 7.42

Scheme 7.43

Scheme 7.44

Scheme 7.45

Scheme 7.46

Scheme 7.47

Scheme 7.48

Scheme 7.49

Scheme 7.50

Scheme 7.51

Scheme 7.52

Scheme 7.53

Scheme 7.54

Scheme 7.55

Chapter 8: Total Syntheses of Natural Products and Biologically Active Compounds by Transition-Metal-Catalyzed C–C Cleavage

Figure 8.1 Biologically active quinones.

Scheme 8.1

Figure 8.2 Pseudolaric acid B.

Scheme 8.2

Figure 8.3 Naturally-occurring hexahydropyrrole[2,3-

b

]indoles.

Scheme 8.3

Figure 8.4 Biologically active benzobicyclo[2.2.2]octenes.

Scheme 8.4

Scheme 8.5

Scheme 8.6

Figure 8.5 (-)-Herbertenol.

Scheme 8.7

Scheme 8.8

Scheme 8.9

Figure 8.6 Cyanthiwigin F.

Scheme 8.10

Scheme 8.11

Scheme 8.12

Scheme 8.13

Scheme 8.14

Scheme 8.15

Scheme 8.16

List of Tables

Chapter 2: Reactions of Three-Membered Ring Compounds

Table 2.1 Rearrangement of bicyclopentanes

Table 2.2 Ring-opening functionalizations of donor–acceptor cyclopropanes

Table 2.3 Ring-opening functionalizations of MCPs. (pin: pinacolato.)

Table 2.4 Transition-metal-catalyzed annulation of MCPs

Table 2.5 Ni-catalyzed annulation of ethyl cyclopropylideneacetate

Table 2.6 Ag-catalyzed reactions of benzocyclopropene with unsaturated hydrocarbons

Chapter 3: Reactions of Four-Membered Ring Compounds

Table 3.1 Transition-metal-catalyzed ring-opening functionalization of biphenylene

Table 3.2 Rh(I)-catalyzed arylative ring opening of cyclobutanones

Chapter 6: Reactions via Cleavage of Carbon–Carbon Bonds of Ketones and Nitriles

Table 6.1 Nickel-catalyzed cross-coupling of nitriles

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Edited by Masahiro Murakami and Naoto Chatani

Cleavage of Carbon–Carbon Single Bonds by Transition Metals

The Editors

Prof. Dr. Masahiro Murakami

Kyoto University

Department of Synthetic Chemistry and Biological Chemistry

Katsura

Kyoto 615-8510

Japan

Prof. Dr. Naoto Chatani

Osaka University

Department of Applied Chemistry

Suita

Osaka 565-0871

Japan

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Preface

A number of transformations are currently available for organic compounds. Mechanistically, most reactions are related to their π-bonds (e.g., C=C, C=O) or polar σ-bonds (e.g., C–Br, C–Li). The frontier orbitals of those bonds are energetically as well as sterically accessible for interaction with other orbitals. On the other hand, the frontier orbitals of nonpolar σ-bonds like C–H and C–C bonds are, in general, much less accessible both energetically and sterically (See Chapter 1 for details). They remain intact under most conventional reaction conditions. Nonetheless, it would provide more straightforward synthetic pathways if a specific one among the ubiquitous nonpolar σ-bonds was selectively cleaved and directly employed for construction and/or functionalization of organic skeletons.

In 1993, Prof. Shinji Murai and his coworkers reported a selective addition reaction of an aromatic C–H bond across a C–C double bond catalyzed by ruthenium, demonstrating the feasibility, and the synthetic potential, of metal-catalyzed cleavage of nonpolar σ-bonds. Since then, a number of catalytic transformations of nonpolar σ-bonds have been developed and even applied to the synthesis of complex natural products and functional materials. This book focuses on transition-metal-mediated and -catalyzed reactions involving C–C bond cleavage. It consists of eight chapters. The first chapter deals with fundamental reactions (stoichiometric reactions) on C–C bond cleavage. This chapter serves as the basis for understanding the mechanisms of the complex catalytic reactions described in Chapters 2–7. Chapter 8 exemplifies applications of C–C bond cleavage reactions to total syntheses of natural products and biologically active molecules.

Each chapter is written by a distinguished chemist who has made a significant contribution to the progress of the chemistry related to C–C bond activation. I would like to thank all the authors for their enormous efforts for this book project. I also appreciate the staff of the editorial team of Wiley-VCH for their continuous help. I hope this book assists the readers to overview this emerging field of chemistry, and also inspires new ideas for the reader's own endeavors in the future.

Kyoto, April 2015

Masahiro Murakami

List of Contributors

Naoki Ishida

Kyoto University

Department of Synthetic Chemistry and Biological Chemistry

Katsura

Nishikyo-ku

Kyoto 615-8510

Japan

Takanori Matsuda

Tokyo University of Science

Department of Applied Chemistry

1-3 Kagurazaka

Shinjuku-ku

Tokyo 162-8601

Japan

Masahiro Miura

Osaka City University

Department of Applied Chemistry

Faculty of Engineering

2-1 Yamada-oka

Suita

Osaka 565-0871

Japan

Masahiro Murakami

Kyoto University

Department of Synthetic Chemistry and Biological Chemistry

Katsura

Nishikyo-ku

Kyoto 615-8510

Japan

Tetsuya Satoh

Osaka City University

Department of Chemistry

Graduate School of Science

3-3-138 Sugimoto

Sumiyoshi-ku

Osaka 558-8585

Japan

and

Osaka City University

Department of Applied Chemistry, Faculty of Engineering

2-1 Yamada-oka

Suita

Osaka 565-0871

Japan

Mamoru Tobisu

Osaka University

Department of Applied Chemistry

Center for Atomic and Molecular Technologies

Graduate School of Engineering

2-1 Yamada-oka

Suita

Osaka 565-0871

Japan

Hideki Yorimitsu

Kyoto University

Department of Chemistry

Graduate School of Science

Kitashirakawa Oiwake-cho

Sakyo-ku

Kyoto 606-8502

Japan

Chapter 1Fundamental Reactions to Cleave Carbon–Carbon σ-Bonds with Transition Metal Complexes

Masahiro Murakami and Naoki Ishida

1.1 Introduction

Transition metal-catalyzed reactions proceed through multiple elementary steps in general and, consequently, the mechanisms are often complicated, especially when backbone structures are reconstructed through a sequence of cleavage and formation of C–C bonds. A step-by-step understanding of elementary steps would be valuable to understand such catalytic transformations. This chapter focuses on elementary steps during which carbon–carbon σ-bonds are cleaved by means of organometallic complexes.

An elementary step to cleave C–C bonds is a reverse process of a C–C bond forming process. Oxidative addition of a C–C bond to a low-valent transition metal complex is a reverse process of reductive elimination, which occurs with a high-valent diorganometal, forming a C–C bond. β-Carbon elimination is a reverse process of insertion of an unsaturated bond into a carbon–metal bond, that is, carbometallation, or 1,2-addition of an organometal across a double bond. Such fundamental reactions are described along with typical examples. Besides this chapter, there are some excellent reviews on C–C bond cleavage available [1].

1.2 Oxidative Addition

Oxidative addition is insertion of a metal into a covalent bond. It involves formal two-electron oxidation of the metal center or one-electron oxidation of two metal centers (Scheme 1.1).

Scheme 1.1

Oxidative addition offers a direct method to cleave a covalent bond. Although a wide variety of bonds, such as C–I and C–Br, are known to facilely undergo oxidative addition reactions to low-valent transition metal complexes, examples of oxidative addition of C–C single bonds are far more rare. The scarcity is in part associated with the thermodynamic stability of C–C bonds. Whereas oxidative addition of C–Br and C–I bonds to low-valent metals is thermodynamically favored in general, that of a C–C single bond is often thermodynamically disfavored.

The kinetic reason for the difficulty in breaking C–C single bonds is the constrained directionality of their σ-orbital. Figure 1.1 shows the interaction of a metal orbital with a C–C single bond. The interactions with C–C double bonds and C–H single bonds are also depicted for comparison. The π-orbital of a C–C double bond is oriented sideways, and thus it interacts with a metal orbital without significant strain and severe steric repulsion. The σ-orbital connecting hydrogen and carbon atoms lies along the bond axis and the directionality is less matched with the metal orbital. However, the constituent 1s orbital of the hydrogen atom is spherical, and can interact with a metal orbital from any direction without distortion. The hydrogen atom has no other substituents except the bonded carbon, thus sterically rendering the direct approach of the metal center less cumbersome. On the other hand, the σ-orbital of a C–C single bond possesses high directionality along the bond axis. Moreover, there are several substituents on both ends, which sterically prevent the approach of metal orbitals. Thus, interaction of such a C–C σ-orbital with a metal orbital is much more difficult than those of a C–C double bond and a C–H bond. Not only the thermodynamic stability, but also this kinetic barrier renders C–C σ-bonds considerably inert.

Figure 1.1 Orbital interactions of a metal with C=C, C−H, C−C bonds.

Despite the intrinsic difficulties mentioned above, a number of strategies have been devised to realize oxidative addition of C–C σ-bonds. For example, release of ring strain of a substrate molecule affords both kinetic and thermodynamic drive for oxidative addition. A chelating effect also assists both kinetically and thermodynamically. Aromatization is also exploited as the driving force for oxidative addition of a C–C bond. Each case is exemplified in the following sections.

1.2.1 Oxidative Addition Utilizing Ring Strain

The orbitals of cyclopropane C–C bonds form “banana bonds”, which protrude away from the bond axis between the two carbon atoms (Figure 1.2). Consequently a metal center can interact with them similarly, to some extent, to the case of a metal–olefin interaction. This interaction lowers the kinetic barrier of the C–C oxidative addition. In addition, the enlargement of the three-membered cyclopropane ring to a four-membered metallacyclobutane relieves the structural strain owing to its constrained bond angles. Thus, the use of cyclopropanes as substrates for oxidative addition of C–C bonds is advantageous both kinetically and thermodynamically.

Figure 1.2 Orbital interactions of a metal with a C−C bond of cyclopropane.

In fact, PtCl2 reacted with cyclopropane to form platinacyclobutanes (Scheme 1.2) [2]. Cyclopropanes substituted with more electron-donating groups reacted faster and cyano and keto-substituted cyclopropanes remained intact [3].

Scheme 1.2

It is often observed that C–H activation precedes C–C activation. For instance, photoirradiation of Cp*Rh(PMe3)(H2) generated coordinatively unsaturated Cp*Rh(PMe3) with liberation of dihydrogen (Scheme 1.3) [4]. The rhodium complex reacted with cyclopropane at −60 °C to furnish a C–H oxidative addition product. No cleavage of a C–C bond was observed at this low temperature. Upon raising the temperature to 0–10 °C, the cyclopropylrhodium rearranged to a rhodacyclobutane. This result indicates that oxidative addition of a C–H bond is kinetically favored and oxidative addition of a C–C bond is thermodynamically favored in this case. The kinetic preference for the oxidative addition of the C–H bond demonstrates the greater steric accessibility of the C–H bond compared with the C–C bond. The analogous rearrangement of a (cyclobutyl)(hydride)rhodium complex into rhodacyclopentane has also been reported [5].

Scheme 1.3

Oxidative addition would proceed via coordination of the σ-bond to the metal (agostic interaction). A rhodium complex with an agostic interaction between a cyclopropane C–C σ-bond and a rhodium center has been reported (Figure 1.3) [6]. The bond lengths of Rh–C3 and Rh–C4 are 2.352 and 2.369 Å, longer than typical Rh–C single bonds, but within the sum of the van der Waals radii of Rh and C. The C3–C4 bond (1.6 Å) is longer than typical cyclopropane C–C bonds (about 1.5 Å), but again within the sum of the van der Waals radii of two carbons. The bonding between Rh and C3–C4 indicates that it might be the precursory structure for oxidative addition of cyclopropane C–C bonds.