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synthesis by NHC‐catalyzed formal [4+2]...Scheme 5.24 Spirooxindole lactams synthesis by NHC‐catalyzed annulation with...Scheme 5.25 Chiral NHC‐catalyzed annulation involving isatin‐derived enals....Scheme 5.26 Stereoselective annulation of isatin‐derived enals with α,β‐unsa...Scheme 5.27 Chiral NHC‐catalyzed asymmetric Michael/aldol/lactonization casc...Scheme 5.28. NHC‐catalyzed annulation with 3‐aminooxindoles or 3‐hydroxyoxin...Scheme 5.29. Tertiary amine‐H bond donor‐catalyzed asymmetric annulation inv...Scheme 5.30. Asymmetric intramolecular [1,5]‐electrocyclization of functiona...Scheme 5.31 Asymmetric annulation of isatin imine by tertiary amine‐H bondin...Scheme 5.32 Asymmetric annulation of methyleneindolinones via double Michael...Scheme 5.33 Asymmetric annulation of methyleneindolinones via Michael‐initia...Scheme 5.34 Asymmetric annulation using isatylidene malononitriles as C2 syn...Scheme 5.35 Asymmetric annulation using isatylidene malononitriles as C3 syn...Scheme 5.36 Asymmetric annulation involving isatin‐derived β,γ‐unsaturated α...Scheme 5.37 Asymmetric annulation involving C3 alkyl ester‐substituted oxind...Scheme 5.38 Asymmetric annulation involving 3‐allyloxindoles.Scheme 5.39 Asymmetric annulation involving 3‐isothiocyanato oxindoles.Scheme 5.40 Asymmetric [4+1] cyclization of 3‐chlorooxindoles with o‐QMs....Scheme 5.41 Asymmetric cyclopropanation of 3‐unsubstituted oxindoles with α‐...Scheme 5.42 One‐pot Michael/Michael/aldol tandem reaction involving 3‐unsubs...Scheme 5.43 Asymmetric desymmetrization of spiro cyclohexadienone oxindoles....Scheme 5.44 Enantioselective Diels–Alder reaction of methyleneindolinones wi...Scheme 5.45 Asymmetric [3+2] cycloaddition of methyleneindolinone and nitron...Scheme 5.46 Asymmetric MCR of diazooxindoles, nitrosoarenes, and nitroalkene...Scheme 5.47 Enantioselective cyclization reaction of isatin and 2‐aminobenza...Scheme 5.48 Asymmetric three‐component 1,3‐dipolar cycloaddition by phosphor...Scheme 5.49 Asymmetric three‐component 1,3‐dipolar cycloaddition.Scheme 5.50 Asymmetric three‐component 1,3‐dipolar cycloaddition.Scheme 5.51 Chiral phosphoric acid‐catalyzed cycloaddition with methyleneind...Scheme 5.52 [3+2] Cycloaddition of isatin‐derived 3‐indolylmethanols and 2‐v...Scheme 5.53 Chiral phosphoric acid‐catalyzed kinetic resolution of racemic s...Scheme 5.54 Asymmetric double Michael cascade reaction of 3‐alkenyloxindoles...Scheme 5.55 Enantioselective 1,3‐dipolar cycloaddition of 3‐alkenyloxindoles...Scheme 5.56 Intramolecular C‐acylation of 3‐substituted oxindoles 320 by PTC...Scheme 5.57 Enantioselective direct intramolecular C(sp2)–H/C(sp3)–H oxidati...Scheme 5.58 Chiral organoiodine‐catalyzed oxidative dearomatization of pheno...

      6 Chapter 6Figure 6.1 Some representative examples of biologically active natural and s...Scheme 6.1 Overman’s approach to (−)‐spirotryprostratin B.Scheme 6.2 Catalytic asymmetric intramolecular Heck synthesis of a spirocycl...Scheme 6.3 Takemoto’s tandem cycloamidation of 2‐(butadienyl)phenylcarbamoyl...Scheme 6.4 Takemoto’s racemic synthesis of spirooxindole alkaloids elacomine...Scheme 6.5 Spirocyclization of α‐substituted tosylamines and proposed mechan...Scheme 6.6 Reductive Heck cyclization in Carreira’s synthesis of gelsemoxoni...Scheme 6.7 Pd(0)‐catalyzed spirooxindole synthesis from isatin‐derived Morit...Scheme 6.8 Enantioselective synthesis of 2‐oxindole spirofused lactones by a...Scheme 6.9 Enantioselective synthesis of 2‐oxindole spirofused lactams by a ...Scheme 6.10 Charette’s synthesis of spiro 3,3′‐cyclopropyloxindoles by silve...Scheme 6.11 Oxidation of N‐aryl‐2‐oxocycloalkane‐1‐carboxamides with Mn(OAc)Scheme 6.12 Aluminum‐promoted cyclization in Trost’s asymmetric synthesis of...Scheme 6.13 Córdova’s asymmetric synthesis of polysubstituted spirocyclic ox...Scheme 6.14 Proposed catalytic cycle for Córdova’s asymmetric synthesis of p...Scheme 6.15 Iron(II)‐catalyzed asymmetric intramolecular aminohydroxylation ...Scheme 6.16 Rhodium(II)‐catalyzed cyclopropanation of 3‐diazo‐2‐oxindole 38....Scheme 6.17 Rhodium(II)‐catalyzed cyclopropanation of 3‐diazo‐2‐oxindole 38....Scheme 6.18 Arai’s rhodium(II)‐catalyzed asymmetric cyclopropanation of 3‐di...Scheme 6.19 Zhou’s mercury(II)‐catalyzed asymmetric cyclopropanation of 3‐di...Scheme 6.20 Zhou’s gold(I)‐catalyzed asymmetric cyclopropanation of 3‐diazo‐...Scheme 6.21 Feng’s magnesium(II)‐catalyzed asymmetric cyclopropanation of al...Scheme 6.22 Feng’s scandium(III)‐catalyzed asymmetric cycloaddition of disub...Scheme 6.23 Carreira’s MgI2‐catalyzed ring expansion of spiro(cyclopropane‐1...Scheme 6.24 Proposed mechanism for the MgI2‐catalyzed reaction of spiro(cycl...Scheme 6.25 Ring expansion of a spiro(cyclopropane‐1,3′‐oxindole) in the syn...Scheme 6.26 Ring expansion of a spiro(cyclopropane‐1,3′‐oxindole) in Carreir...Scheme 6.27 Ring expansion of a spiro(cyclopropane‐1,3′‐oxindole) in Carreir...Scheme 6.28 Carboxylative Pd‐catalyzed TMM cycloaddition to an isopropyliden...Scheme 6.29 Enantioselective carboxylative Pd‐catalyzed TMM cycloaddition to...Scheme 6.30 Enantioselective Cu(I)‐catalyzed 1,3‐dipolar cycloaddition of az...Figure 6.2 Proposed structure of the tetrahedral complex formed by coordinat...Scheme 6.31 Enantioselective Ag(I)‐catalyzed 1,3‐dipolar cycloaddition of az...Scheme 6.32 Franz’s titanium(IV)‐catalyzed stereoselective synthesis of spir...Scheme 6.33 Franz’s scandium(III)‐catalyzed asymmetric [3+2] annulation of a...Scheme 6.34 Franz’s enantioselective allylsilane annulation and C–Si oxidati...Scheme 6.35 Franz’s titanium(IV)‐catalyzed diastereoselective synthesis of s...Scheme 6.36 Franz’s scandium(III)‐catalyzed enantioselective synthesis of a ...Scheme 6.37 Franz’s scandium(III)‐catalyzed enantioselective [3+2] carboannu...Scheme 6.38 Franz’s scandium(III)‐catalyzed enantioselective [3+2] carboannu...Scheme 6.39 Feng’s magnesium(II)‐catalyzed enantioselective [3+2] cycloaddit...Scheme 6.40 Lu’s palladium(0)‐catalyzed enantioselective [3+2] cycloaddition...Scheme 6.41 Proposed mechanism for the palladium(0)‐catalyzed enantioselecti...Scheme 6.42 Mei’s palladium(0)‐catalyzed enantioselective [3+2] cycloadditio...Scheme 6.43 Du’s rhodium(0)‐catalyzed enantioselective [3+2] cycloaddition o...Scheme 6.44 Asymmetric one‐pot sequential organo‐ and gold(I)‐catalyzed Mann...Scheme 6.45 Trost’s dinuclear zinc‐catalyzed asymmetric spiroannulation reac...Scheme 6.46 Kanai–Matsunaga’s strontium‐catalyzed asymmetric synthesis of 3‐...Scheme 6.47 Chen‐Xiao’s zinc(II)‐catalyzed enantioselective cascade Michael ...Scheme 6.48 Yan‐Zhou’s nickel(II)‐catalyzed diastereo‐ and enantioselective ...Scheme 6.49 Ashfeld’s rhodium‐catalyzed formal [4+1] cycloaddition route to ...Scheme 6.50 Ashfeld’s rhodium‐catalyzed formal [4+1] cycloaddition syntheses...Scheme 6.51 Lin‐Feng’s zinc‐catalyzed asymmetric Diels–Alder reaction of a B...Scheme 6.52 Kumar’s dysprosium‐catalyzed asymmetric hetero‐Diels–Alder react...Scheme 6.53 Kumar’s magnesium‐catalyzed asymmetric hetero‐Diels–Alder reacti...Scheme 6.54 Tanaka’s enantioselective synthesis of spirocyclic benzopyranone...Scheme 6.55 Shintani–Hayashi’s stereoselective synthesis of spirocyclic oxin...Scheme 6.56 Proposed catalytic cycle for the palladium‐catalyzed decarboxyla...Scheme 6.57 Liu–Feng’s nickel‐catalyzed asymmetric aza‐Diels–Alder reaction ...Scheme 6.58 Liebeskind’s enantioselective synthesis of spirooxindoles based ...Scheme 6.59 Feng’s cobalt‐catalyzed asymmetric Darzens reaction of phenacyl ...Scheme 6.60 Wang’s zinc‐catalyzed enantioselective desymmetrization/cyclizat...Scheme 6.61 Shanmugam’s copper(I)‐catalyzed one‐pot, three‐component diaster...Scheme 6.62 A plausible mechanism of the copper(I)‐catalyzed three‐component...

      7 Chapter 7Scheme 7.1 Synthesis of spiropyrrolidines by Mikami.Scheme 7.2 Asymmetric construction of a dispiropyrrolidine by Yu and Deng....Scheme 7.3 Silver phosphate‐catalyzed asymmetric intramolecular dearomatizat...Scheme 7.4 Enantioselective [4+1] spiroannulation catalyzed by Rh.Scheme 7.5 Chiral phosphine‐catalyzed synthesis of spiropyrrolidines reporte...Scheme 7.6 Organocatalyzed asymmetric formal [3+2] cycloaddition of isocyano...Scheme 7.7 The combination photoredox and primary amine catalysis used at th...Scheme 7.8 Enantioselective synthesis of spiroindolenines reported by You....Scheme 7.9 Enantioselective construction of spiroindolenines catalyzed by Pd...Scheme 7.10 Enantioselective synthesis of spiroindolines by intramolecular d...Scheme 7.11 Enantioselective organocatalyzed cascade reactions to spiroindol...Scheme 7.12 Application of chiral phosphoric acid for the preparation of spi...Scheme 7.13 Oxidative N‐heterocyclic carbene catalyzed dearomatization of in...Scheme 7.14 Enantioselective access to gem‐difluorinated spiroindolines.Scheme 7.15 Enantioselective synthesis of spiroindolines via cascade reactio...Scheme 7.16 Enantioselective

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