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Tandem reactions of Pd‐catalyzed cross‐coupling of 3‐(2‐isocyanoethyl)indoles with diazoacetates and subsequent spirocyclization/Mannich‐type reaction have been developed to assemble polycyclic spiroindoline skeletons. Formation of spiroindolenines has been proven as the crucial step for the following Mannich‐type cyclization reaction. Accordingly, a novel approach on chiral phosphoric acid catalyzed Mannich‐type cyclization toward the formation of diastereomerically and enantiomerically enriched pentacyclic spiroindolines has been established. Moreover, the products of the reaction are versatile building blocks in synthetic chemistry, as demonstrated by the synthesis of the key framework of aspidosperma and kopsia alkaloids.

Copper salts, which are abundant, relatively inexpensive and possess low toxicity,h ave long been useda sv ersatile catalysts for various reactions in organic synthesis.R ecently,t he development of Cu-catalyzed or -mediated C À Hf unctionalization reactions has gaineds ignificant attention. Since the pioneering work of Daugulis on the introduction of 8-aminoquinoline and picolinic acid auxiliariesa sr emovable directing groups in transitionm etal-catalyzed C À Hb onda ctivations,t he combination of copper saltsw ith these bidentated irecting groups has emerged as an innovatives trategyf or the construction of carbon-carbon or carbon-heteroatom bonds through C À Hb ond cleavage.I na ddition to the 8-aminoquinoline and picolinamides ystems,s everal other bidentate directing groups including the 2-aminophenyloxazoline group by Yu andD ai andt he PIP systemb yS hi, have been developeda sw ell. This review intends to cover most of the recent advances on copper-catalyzed or -mediatedd irect sp 2 and sp 3 C À Hb ondf unctionalizations assisted by these bidentate directing groups.T he major achievements in this area are discussed and catalogued by the type of bonds formed (C À C, C À O, C À N, C À S, C À Pe tc.). Special attention is paid to the reaction mechanisms.S electede xamples of substrates are listed as well. In addition, apersonal outlook is given at the end.1I ntroduction 2C À CB ond Formation 3C À OB ond Formation 4C À NBond Formation 5C À SBond Formation 6C À PBondF ormation 7C À X(X= F, Cl, Br,I )BondF ormation 8I ntermolecularC À HA ctivation-Cyclization Tandem Reactions 9S ummary andOutlook

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