Spiro Compounds

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 MgI 2‐catalyzed ring expansion of spiro(cyclopropane‐1...Scheme 6.24 Proposed mechanism for the MgI 2‐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 synthesis of spirobilactams reported by Cai....Scheme 7.17 Enantio‐ and diastereoselective Pd‐catalyzed carbocyclization ca...Scheme 7.18 Pd‐catalyzed asymmetric intramolecular arylative dearomatization...Scheme 7.19 Iridium‐catalyzed intramolecular asymmetric allylic dearomatizat...Scheme 7.20 Enantioselective organocatalyzed formal [3+3] spiroannulation re...Scheme 7.21 NHC‐catalyzed enantioselective synthesis of spiropiperidinones r...Scheme 7.22 Asymmetric dearomative formal [4+2] cycloadditions published by ...Scheme 7.23 Enantioselective ene‐type spirocyclization developed by Mikami....Scheme 7.24 Enantioselective 1,6‐conjugate addition/annulation of para‐quino...Scheme 7.25 Enantioselective synthesis of spirodihydrofuranes developed by S...Scheme 7.26 The enantioselective synthesis of spirolactones reported by Gade...Scheme 7.27 Asymmetric copper‐catalyzed preparation of spirotetrahydropyrane...Scheme 7.28 Enantioselective dearomatization of phenols using chiral hyperva...Scheme 7.29 Chiral hypervalent organoiodine‐catalyzed enantioselective oxida...Scheme 7.30 Enantioselective oxidative dearomatization of arenols using chir...Scheme 7.31 Asymmetric synthesis of spiro‐2( 3H )‐furanones via phase‐transfer...Scheme 7.32 Enantioselective construction of spirocyclic benzofuranone cyclo...Scheme 7.33 Asymmetric tandem synthesis of spirocyclic (2H)‐dihydrobenzofura...Scheme 7.34 The enantioselective synthesis of spirobenzofuranones reported b...Scheme 7.35 The catalytic asymmetric one‐pot [3+2] cyclization/semipinacol r...Scheme 7.36 Reaction mechanism.Scheme 7.37 Organocatalytic synthesis of spirobenzofuranones via cascade Mic...Scheme 7.38 Two approaches to chiral spirocyclic benzofuranones by using ami...Scheme 7.39 The enantioselective approaches leading to spirocyclic compounds...Scheme 7.40 Organocatalytic asymmetric double Michael addition and Michael/a...Scheme 7.41 Asymmetric construction of spirocyclopentenebenzofuranone core s...Scheme 7.42 Application of trienamine catalysis for the construction of spir...Scheme 7.43 Asymmetric synthesis of pyrrolidine‐ and tetrahydrothiophene‐fus...Scheme 7.44 Catalytic asymmetric brominative or chlorinative dearomatization...Scheme 7.45 The synthesis of spiro‐heterocycles by the NHC‐catalyzed annulat...Scheme 7.46 The enantioselective formal [2+1+3] annulation forming spirocycl...Scheme 7.47 Enantioselective ring expansion of vinyl cyclopropanes combining...Scheme 7.48 Catalytic enantioselective synthesis of spirocycles 13.Scheme 7.49 Enantioselective synthesis of spirocyclic benzopyranones by rhod...Scheme 7.50 Enantioselective organometallic approach to chiral spirobenzopyr...Scheme 7.51 Enantioselective synthesis of a‐spirocyclopropyl lactones.Scheme 7.52 Asymmetric synthesis of 3,4‐dihydrocoumarin motif in spirocycle ...Scheme 7.53 Synthesis of highly substituted chiral spirodihydrocoumarins....Scheme 7.54 Organocatalytic tandem Morita–Baylis–Hillman–Michael reaction fo...Scheme 7.55 A chiral squaramide‐catalyzed approach constructing spiro‐3,4‐di...Scheme 7.56 Construction of spiro‐bridged polyheterocyclic compounds.Scheme 7.57 The synthesis of spirocycle compounds via enantioselective organ...Scheme 7.58 Catalytic desymmetrizing dehydrogenation of 4‐substituted cycloh...Scheme 7.59 Enantioselective synthesis of spirocyclic compounds containing b...Scheme 7.60 Asymmetric synthesis of spirocyclic tetrahydrothiophene‐chromano...Scheme 7.61 Enantioselective synthesis of spiro compounds containing tetrahy...Scheme 7.62 Enantioselective construction of polyfunctionalized spiroannulat...Scheme 7.63 A chiral fluoride‐catalyzed asymmetric cascade sulfa‐Michael/ald...Scheme 7.64 Enantioselective synthesis of spirocyclic compounds containing b...Scheme 7.65 Enantioselective synthesis of spirocyclic compounds containing b...Scheme 7.66 The enantioselective approach provides chiral spiro[thiopyranoin...Scheme 7.67 NHC‐catalyzed enantioselective dearomatizing hydroacylation of b...Scheme 7.68 Asymmetric synthesis of spiropyrazolones by complex of rhodium‐c...Scheme 7.69 Enantioselective vinylogous Michael/aldol reaction to synthesize...Scheme 7.70 Highly stereoselective synthesis of spiropyrazolones reported by...Scheme 7.71 The synthesis of unsymmetrical diaryl‐substituted spirocyclohexa...Scheme 7.72 The synthesis of spiropyrazolones via organocatalytic Michael/Mi...Scheme 7.73 Three‐component Michael/Michael/aldol reaction cascade reported ...Scheme 7.74 Asymmetric synthesis of spiropyrazolones through phosphine‐catal...Scheme 7.75 Asymmetric, three‐component, and one‐pot synthesis of spiropyraz...Scheme 7.76 Mechanism of asymmetric, three‐component, one‐pot synthesis of s...Scheme 7.77 Diastereo‐ and enantioselective construction of cyclohexanone‐fu...Scheme 7.78 Lewis‐base‐catalyzed asymmetric [3+3] annulation reaction of Mor...Scheme 7.79 Asymmetric synthesis of spirocyclohexene pyrazolones via formal ...Scheme 7.80 Enantioselective synthesis of pyrazolone‐fused spirocyclohexenol...Scheme 7.81 Diastereodivergent and enantioselective access to spiroepoxides....Scheme 7.82 Synthesis of chiral pyrazolone and spiropyrazolone derivatives t...Scheme 7.83 NHC‐catalyzed asymmetric formal [4+2] annulation to construct sp...Scheme 7.84 Asymmetric synthesis of spiropyrazolones by sequential organo‐ a...Scheme 7.85 Michael/Conia‐ene cascade reaction under synergistic catalysis p...Scheme 7.86 Diastereoselective and enantioselective synthesis of barbiturate...Scheme 7.87 The enantioselective approaches to spirobarbiturates by using ch...Scheme 7.88 Isothiocyanate strategy for the synthesis of spirocyclic barbitu...Scheme 7.89 Palladium‐catalyzed enantioselective synthesis of spirocyclic az...Scheme 7.90 Application of chiral phosphine in organocatalytic synthesis of ...Scheme 7.91 Anderson’s synthesis of spirocyclic azlactones.Scheme 7.92 Formal [3+2] cycloaddition of vinylcyclopropane azlactones to en...Scheme 7.93 Enantioselective access to spirocyclic sultams by chiral Cp x–rho...Scheme 7.94 The synthesis of chiral spirosultams by multi sequential reactio...Scheme 7.95 Asymmetric construction of spirocyclic pyrrolidine‐thiazolidined...Scheme 7.96 The enantioselective cycloaddition of cyclic enones with sultams...Scheme 7.97 Asymmetric construction of spiro thiopyrano‐indole‐benzoisothiaz...Scheme 7.98 Enantioselective synthesis of chiral spirocycles containing rhod...Scheme 7.99 Asymmetric synthesis of highly functionalized spirothiazolidinon...Scheme 7.100 Enantioselective construction of spiro chroman‐thiazolones.Scheme 7.101 Catalytic asymmetric synthesis of aromatic spiroketals.Scheme 7.102 Enantio‐ and diastereoselective spiroketalization catalyzed by ...Scheme 7.103 Asymmetric synthesis of spiroketals and spiroaminals.Scheme 7.104 Chiral phosphoric acid‐catalyzed enantioselective and diastereo...Scheme 7.105 Organohalogenite‐catalyzed spiroketalization.Scheme 7.106 Stereoselective three‐component reaction of salicylaldehydes, a...Scheme 7.107 The enantioselective synthesis spiropyrrolidines containing dih...Scheme 7.108 Asymmetric synthesis of spirocyclic β‐lactams through copper‐ca...Scheme 7.109 Hetero‐Diels−Alder process used for the synthesis of spiropyrro...Scheme 7.110 The enantioselective fluorocyclization catalyzed by chiral BINO...Scheme 7.111 Enantioselective cycloaddition to trisubstituted nitroolefins t...Scheme 7.112 Enantioselective access to dispirooxindoles from furfurylcyclob...Scheme 7.113 The enantioselective synthesis of bis‐spiroketals.Scheme 7.114 Highly efficient enantioselective synthesis of bispiro benzofur...