From C-H to C-C bonds : cross-dehydrogenative-coupling

330 Pages·2014·51.086 MB·English

by  Chao-Jun Li

From C–H to C–C Bonds
Cross-Dehydrogenative-Coupling
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From C–H to C–C Bonds
Cross-Dehydrogenative-Coupling
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03 Email: [email protected]
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2- Preface
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10. Theabilitytoachieveanygoalsinoursocietyislargelydependentupon,and
oi: limited by, the state-of-the-art tools available. While the speed and ease of
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http:// The development of novel chemical reactivities and reaction conditions
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modification. However, the archetypical requirements of standard classical
chemical transformations are the functional groups, which provide the
platformforchemicalconversionsthathaveledtothesynthesisofmillions
of both naturally existing and non-naturally existing molecules in just less
thantwocenturies,onlyablinkingmomentinhumanhistory.Inspiteofthe
great successes, there are still various shortcomings: the pre-functionalized
startingmaterialsneedtobesynthesizedinseparatesteps,andtheamount
of waste associated with solvent usage, purification and isolation man-
euvers, as well as the required manpower to perform a synthesis increases
exponentially with the number of synthetic steps. With recent concerns re-
garding theadverseeffectsof chemicalproductionprocesses,aswell asthe
RSCGreenChemistryNo.26
FromC–HtoC–CBonds:Cross-Dehydrogenative-Coupling
EditedbyChao-JunLi
rTheRoyalSocietyofChemistry2015
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
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viii Preface
emphasis on green chemistry and chemical sustainability, various frontiers
ofsynthetic chemistryhavebeen explored.Amongthem,theconceptofthe
cross-dehydrogenative-coupling(CDC)reactionwasformulatedin2003.The
directgenerationofaC–CbondfromtwodifferentC–Hbondsconstitutesan
idealthathasgame-changingpotentialinsyntheticdesign.Thesubjecthas
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s.rs 1.2 CDCReactionsInvolvingsp3C–HBondsandspC–H
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p:// 1.2.1 Reaction of sp3 C–H Bonds Adjacent to
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4 o 1.2.2 Asymmetric Reaction of sp3 C–H Bonds
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9:26. August 1.2.3 ROexaygcteinon of sp3 C–H Bonds Adjacent to 6
11:1n 19 1.2.4 Reaction of Benzylic sp3 C–H Bonds 7
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Nitrogen 7
1.3.2 Reaction of sp3 C–H Bonds Adjacent to
Oxygen 9
1.3.3 Reaction of Benzylic and Allylic sp3 C–H
Bonds 9
1.3.4 Reaction of a-sp3 C–H Bonds of Carbonyl
Groups 10
1.3.5 Reaction of Alkane sp3 C–H Bonds 11
1.4 CDC Reactions Involving sp3 C–H Bonds and
sp3 C–H Bonds 15
1.4.1 Reaction of sp3 C–H Bonds Adjacent to
Nitrogen 15
RSCGreenChemistryNo.26
FromC–HtoC–CBonds:Cross-Dehydrogenative-Coupling
EditedbyChao-JunLi
rTheRoyalSocietyofChemistry2015
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
ix
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x Contents
1.4.2 Reaction of sp3 C–H Bonds Adjacent to
Oxygen 17
1.4.3 Reactions with Allylic and Benzylic C–H
Bonds 18
1.4.4 Reactions with Alkanes 19
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11:1n 19 Chapter 3 CReoapcpteior-nCsatalyzed Cross-Dehydrogenative-Coupling 55
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3.2 Copper-Catalyzed CDC Reactions Involving C–H
Bonds Adjacent to Nitrogen 56
3.2.1 sp3 C–H Bonds and sp C–H Bonds 56
3.2.2 sp3 C–H Bonds and sp2 C–H Bonds 57
3.2.3 sp3 C–H Bonds 59
3.3 Copper-Catalyzed CDC Reactions Involving C–H
Bonds Adjacent to Oxygen 60
3.4 Copper-Catalyzed CDC Reactions Involving Other
C–H Bonds 61
3.4.1 Allylic C–H Bonds 61
3.4.2 Benzylic C–H Bonds 61
3.4.3 C–N Bond Formation 62
3.4.4 C–P Bonds 62
3.5 Asymmetric CDC Reactions 63
3.6 Summary and Outlook 64
References 65