9Scheme 9.1 Intramolecular dearomative reaction of para‐substituted phenol.Scheme 9.2 Proposed dearomative reaction pathway.Scheme 9.3 Preliminary enantioselective construction of all‐carbon spirocent...Scheme 9.4 Synthesis of spiro[4.5]decane core architecture via dearomative s...Scheme 9.5 Iridium‐catalyzed asymmetric allylic dearomatization of phenols....Scheme 9.6 C‐alkylation for ortho‐substituted naphthols.Scheme 9.7 Intramolecular dearomative reaction of alkyne‐substituted phenol....Scheme 9.8 Intermolecular dearomative spiroannulation of phenol and iodobenz...Scheme 9.9 Strategy for dearomative arylation of phenols.Scheme 9.10 Preliminary results of asymmetric dearomative arylation of pheno...Figure 9.1 Natural erythrina alkaloids.Scheme 9.11 Pd(0)‐catalyzed intramolecular arylative coupling of 5‐hydroxyl ...Scheme 9.12 Preliminary asymmetric studies for constructing erythrinane skel...Scheme 9.13 Proposed one‐step construction of spirocarbocycles and potential...Scheme 9.14 A DYKAT of phenolic derivative via axial‐to‐central chirality tr...Scheme 9.15 Palladium‐catalyzed dynamic kinetic asymmetric transformation.Scheme 9.16 [3+2] Spiroannulation of phenol‐derived biaryls and diynes.Scheme 9.17 Formal [2+2+1] cycloaddition routes to new tricycles.Scheme 9.18 RuII‐catalyzed dearomative spiroannulation of naphthols via C(spFigure 9.2 Proposed mechanism of C–H bond activation/dearomative reaction.Scheme 9.19 Spiroannulation of 2‐arylphenols via C–H activation/dearomative ...Scheme 9.20 Pd‐catalyzed oxidative dearomatization of free naphthols.Scheme 9.21 [2+2+1] Spiroannulation of unsymmetrical alkynes.Scheme 9.22 Spirocyclopentadienes of 2‐alkenylphenols and alkynes.Scheme 9.23 Spirocyclopentadienes of 2‐alkenylphenols and conjugated enynes....Scheme 9.24 Three‐component dearomatizing [2+2+1] spiroannulation.Scheme 9.25 Preliminary studies on the synthetic application of dearomatizin...Scheme 9.26 Pd/NBE‐catalyzed C–H activation/arene dearomatization reaction....Scheme 9.27 [4+1] Spiroannulation by C(sp3)‐H activation and naphthol dearom...Scheme 9.28 Ir‐catalyzed asymmetric allylic alkylation for constructing spir...Scheme 9.29 Allylic dearomatization for the synthesis of spiro cyclopentene‐...Figure 9.3 The energetic barrier of transition states.Scheme 9.30 Dearomative arylation of indoles for spiroindolenine derivatives...Scheme 9.31 Dearomatization of C2‐substitued indoles for spirooxindoles.Scheme 9.32 Synthesis of the core structure of phalarine.Scheme 9.33 Process of gold‐catalyzed intramolecular alkyne hydroarylation....Scheme 9.34 Dearomatization of aromatic ynones for spirocyclic scaffolds.Scheme 9.35 One‐pot spirocyclization/trapping to form tetracycles.Scheme 9.36 Scaffolds for the synthesis of spirocyclic indole derivatives.Scheme 9.37 Intermolecular spirocyclization of indoles and propargyl carbona...Figure 9.4 Novel spiroindolenine products.Scheme 9.38 Stepwise synthesis spirocyclic indolines of indoles with allyl a...Scheme 9.39 Pd/NBE‐catalyzed intermolecular dearomative spiroannulation of i...Figure 9.5 Proposed reaction mechanism for palladium‐catalyzed dearomatizati...Scheme 9.40 Asymmetric cycloadditions of vinylcyclopropanes with indoles.Scheme 9.41 Allylic dearomatization of pyrroles for six‐membered spiro‐2H‐py...Scheme 9.42 Arylative dearomatization of pyrroles for six‐membered spiro‐2H‐...Figure 9.6 Selected bioactive compounds bearing spironaphthalene‐pyrrolidine...Scheme 9.43 Allylic dearomatization of pyrroles for five‐membered spiro‐2H‐p...Figure 9.7 Quantitative formation of spirocycles from 3‐pyrroles.Scheme 9.44 Intramolecular nucleophilic dearomatization of furans.Scheme 9.45 Dearomatizing 2,5‐alkoxyarylation of furan rings for spirooxindo...Scheme 9.46 Three possible pathways for the formation of 142a.Scheme 9.47 Mechanistic experiments for dearomatizing 2,5‐alkoxyarylation of...Scheme 9.48 Further transformations of spiro π‐allyl palladium.Scheme 9.49 Synthesis of spiroacetals from boronic acids and hydroxyalkylfur...Scheme 9.50 Synthesis of thiophene‐containing spirocyclic products via C–H a...Scheme 9.51 Cu(II)‐promoted transformations of α‐thienylcarbinols into spiro...Scheme 9.52 Synthesis of halogenated spirothienooxindoles from 159a and 158aScheme 9.53 Intermolecular Heck‐type dearomative [2+2+1] spiroannulation of ...Scheme 9.54 Palladium‐catalyzed aryne insertion/arene dearomatization to spi...Scheme 9.55 Mechanism studies for the 5‐exo‐trig spiroannulation...Scheme 9.56 Intramolecular asymmetric allylic dearomatization of benzene der...Scheme 9.57 A Cu‐catalyzed Sommelet–Hauser dearomatization of dihydrophenant...Scheme 9.58 Substituent effects.
10 Chapter 10Figure 10.1 Fenestrane motifs and their multifariousness. Top: (a) A stylist...Figure 10.2 From spiranes to fenestranes and beyond. Top: Spiro[4.4]nonane (Scheme 10.1 Retrosynthetic approach to the [5.5.5.5]fenestrane skeleton from...Figure 10.3 Systematic extensions of Keese’s parent all‐cis‐[5.5.5.5]fenestr...Scheme 10.2 Keese’s first synthesis of all‐cis‐[5.5.5.5]fenestrane (2).Scheme 10.3 Cook’s first‐reported synthesis of all‐cis‐[5.5.5.5]fenestra‐2,5...Scheme 10.4 Three hypothetical functionalized spiro structures as starting p...Scheme 10.5 Synthesis of 1,3‐indanediol 24 and [2,2′]spirobiindane‐1,1′‐diol...Scheme 10.6 Attempted construction of the benzoannelated [5.6.6.6]fenestrane...Scheme 10.7 Synthesis of the benzoannelated [5.5.5.6]fenestranes with cis,ci...Scheme 10.8 Unsuccessful attempts to synthesize fenestrindane 7 along the fu...Scheme 10.9 Naphthoannelated all‐cis‐[5.5.5.6]fenestranones 51 and 53‐55 acc...Figure 10.4 The first benzoannelated [5.5.5.6]fenestranones bearing two (56)...Scheme 10.10 Construction of extended benzoannelated fenestrane derivatives ...Scheme 10.11 Top: Both the stereoisomeric tetramethyl‐substituted [5.5.5.6]f...Scheme 10.12 Synthesis of the bis‐(pentaarylphenyl)fenestrindane 82 from the...Scheme 10.13 Synthesis of saddle‐shaped fourfold bay‐bridged fenestrindane 9...Figure 10.5 The parent fenestrindane saddle 10 and its octamethoxy derivativ...Figure 10.6 Solid‐state structure of the fourfold bay‐bridged fenestrindane Scheme 10.14 Access to centrohexaindanes via the “broken fenestrane route” a...Figure 10.7 Solid‐state molecular structure of tetramethoxycentrohexaindane Figure 10.8 Selected derivatives of centrohexaindane (9) in a perspective pr...Figure 10.9 The four constitutional isomers of hexanitrocentrohexaindane, 10...Figure 10.10 Dodecafunctionalized centrohexaindanes 105–107, synthesized by ...Figure 10.11 Solid‐state molecular structure of dodecaphenylcentrohexaindane...Figure 10.12 Two hypothetical extensions of the centrohexaindane core, model...
11 Chapter 11Figure 11.1 The different synthesized natural products discussed in this cha...Figure 11.2 The structure of (+)‐calafianin.Figure 11.3 The proposed retrosynthesis for (+)‐calafianin.Scheme 11.1 The synthesis of exocyclic vinyl epoxide 7.Scheme 11.2 The 1,3 dipolar cycloaddition leading to compounds 6 and 11.Scheme 11.3 The synthesis of (+)‐calafianin (1).Figure 11.4 The structure of pseurotin A.Figure 11.5 The retrosynthesis of pseurotin A.Scheme 11.4 The synthesis of 16.Scheme 11.5 The synthesis of pseurotin A.Figure 11.6 The structure of (−)ushikulide A.Figure 11.7 The retrosynthesis of (−)ushikulide A.Scheme 11.6 The synthesis of compounds 33, 34, and 35.Scheme 11.7 The synthesis of compound 30.Scheme 11.8 The synthesis of compound 31.Scheme 11.9 The synthesis of (−)ushikulide A.Figure 11.8 The structure of (−)‐acutamine.Figure 11.9 The proposed retrosynthesis procedure.Scheme 11.10 The synthesis of compounds 60 and 61.Scheme 11.11 The synthesis of compound 59.Scheme 11.12 The synthesis of 58.Scheme 11.13 The synthesis of 77.Scheme 11.14 The synthesis of compound 80.Scheme 11.15 The synthesis of (−)‐acutumine.Figure 11.10 Herzon’s retrosynthesis of (−)‐acutumine.Scheme 11.16 The synthesis of compound 87.Scheme 11.17 The synthesis of compound 95.Scheme 11.18 The synthesis of (−)‐acutumine.Figure 11.11 The structure of spirotryprostatin B.Figure 11.12 The proposed retrosynthesis.Scheme 11.19 The synthesis of compound 101.Scheme 11.20 The synthesis of compounds 109 and 110.Scheme 11.21 The synthesis of (−)‐spirotryprostatin B.Figure 11.13 The retrosynthesis proposed by Carreira.Scheme 11.22 The synthesis of compound 116.Scheme 11.23 The synthesis of compound 115.Scheme 11.24 The synthesis of (−)‐spirotryprostatin B.
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