Regiospecific synthesis of 3,4-disubstituted furans from 3,4-bis(trimethylsilyl) furan.

• Other Authors: Song, Zhi Zhong.
• Format: Others
• Language: English
• Published: Chinese University of Hong Kong 1994
• Subjects: Furans > Synthesis; Furans
• Online Access: http://library.cuhk.edu.hk/record=b5888233; http://repository.lib.cuhk.edu.hk/en/item/cuhk-318199

by Zhi Zhong Song. === Thesis (Ph.D.)--Chinese University of Hong Kong, 1994. === Includes bibliographical references (leaves 158-171 (1st gp)). === Acknowledgements --- p.i === Contents --- p.ii === Abstract --- p.viii === List of Publications Based on Research Reported in this Thesis --- p.ix === List of Acronyms and Abbreviations --- p.x === Chapter Chapter I. --- The Reaction and Synthesis of Furans === Chapter I.1. --- Introduction --- p.1 === Chapter I.2. --- General Survey of Reaction of Furan --- p.2 === Chapter I.2.1. --- Electrophilic substitutions --- p.2 === Chapter I.2.2. --- Nucleophilic reactions --- p.3 === Chapter I.2.3. --- Cycloaddition reactions --- p.5 === Chapter I.2.4. --- Oxidation reactions --- p.7 === Chapter I.2.5. --- Reduction reactions --- p.9 === Chapter I.3 --- New Progress in the Synthesis of Polysubstituted Furans --- p.10 === Chapter I.3.1. --- From carbohydrates --- p.11 === Chapter I.3.2. --- The Passerini-type reaction --- p.11 === Chapter I.3.3. --- "Via γ,δ-unsaturated-β-ketoesters" --- p.12 === Chapter I.3.4. --- Via tantalum-alkyne complex --- p.13 === Chapter I.3.5. --- Via addition of carbenoids --- p.14 === Chapter I.3.6. --- Via cycloaddition of alkyne and isomunchnone --- p.15 === Chapter I.3.7. --- Via reaction of metal carbene complexes with alkynes --- p.17 === Chapter I.3.8. --- Via η2-thiophosphinito complexes of cobalt --- p.18 === Chapter I.3.9. --- Via palladium-catalyzed annelation --- p.19 === Chapter I.3.10. --- "Via α,β- and β,γ-unsaturated ketones" --- p.24 === Chapter I.3.11. --- Via allenes --- p.26 === Chapter I.3.12. --- "Via 2,5-dihydrofurans" --- p.28 === Chapter I.3.13. --- Via radical cyclization --- p.28 === Chapter Chapter II. --- "The Synthesis and Applications of 3,4-Disubstituted Furans" === Chapter II. 1. --- Introduction --- p.30 === Chapter II.2. --- "Synthesis of 3,4-Disubstituted Furans" --- p.30 === Chapter II.2.1. --- Via Diels-Alder/retro-Diels-Alder reaction --- p.30 === Chapter II.2.2. --- "Via 2-butyne-l,4-diol" --- p.31 === Chapter II.2.3. --- Via ylides --- p.31 === Chapter II.2.4. --- "Via 3,4-dimethylsulpholene" --- p.32 === Chapter II.2.5. --- Via functionalized furan ring --- p.33 === Chapter II.2.5.1. --- Via Diels-Alder/retro-Diels-Alder reaction --- p.33 === Chapter II.2.5.2. --- Via furan matathesis --- p.33 === Chapter II.2.5.3. --- Via allene --- p.34 === Chapter II.2.5.4. --- "Via 3,4-disubstituted furans" --- p.35 === Chapter II.2.5.5. --- Via 3-hydroxymethylfuran --- p.36 === Chapter II.3. --- "Some Synthetic Applications of 3,4-Disubstituted Furans" --- p.37 === Chapter II.3.1. --- "Furan-3,4-dicarboxylic acid and its ester" --- p.37 === Chapter II.3.2. --- "3,4-Alkoxyfuran" --- p.39 === Chapter II.3.3. --- "3,4-Dichloromethylfuran" --- p.41 === Chapter II.3.4. --- 4-(Trimethylsilylacetylenyl)-3-(trimethylsilyl)furan --- p.42 === Chapter II.3.5. --- "3,4-Dimethylfuran" --- p.43 === Chapter Chapter III. --- Results and Discussion === Chapter III.1. --- Aim of the Present Work --- p.45 === Chapter III.2. --- ipso-Effect of Silyl Groups --- p.45 === Chapter III.3. --- "Synthesis of 3,4-Bis(trimethylsilyl)furan (105) and Its Modification" --- p.47 === Chapter III.4. --- "Acid-catalyzed Rearrangement of 3,4-Bis(trimethylsilyl)furan (105)" --- p.48 === Chapter III.5. --- "Diels-Alder Reactions of 3,4-Bis(trimethylsilyl)furan (105)" --- p.51 === Chapter III.6. --- "Acylation Reaction of 3,4-Bis(trimethylsilyl)furan (105)" --- p.54 === Chapter III.7. --- "Iodination of 3,4-Bis(trimethylsilyl)furan (105)" --- p.56 === Chapter III.8. --- Synthesis of 4-Substituted-3-(trimethylsiIyl)furan from Palladium- and Nickel-Catalyzed Cross-Coupling Reaction of 4-Iodo-3-(trimethylsilyl)furan (120) --- p.57 === Chapter III.8.1. --- Introduction --- p.57 === Chapter III.8.2. --- Heck-type reaction of 4-iodo-3-(trimethylsilyl)furan (120) --- p.59 === Chapter III.8.2.1. --- General feature of Heck reaction --- p.59 === Chapter III.8.2.2. --- Palladium-catalyzed cross-coupling of 4-iodo-3- (trimethylsilyl)furan (120) with terminal alkenes --- p.61 === Chapter III.8.2.3. --- Mechanism of result --- p.62 === Chapter III.8.2.4. --- "Synthesis of 3-(trimethylsilyl)-5,6- bis(ethoxycarbonyl)benzo[2.3-b]furan (126) from Heck- type reaction of 4-iodo-3-(trimethylsilyl)furan (120) and ethyl acrylate" --- p.63 === Chapter III.8.3. --- Stille-type reaction of 4-iodo-3-(trimethylsilyl)furan (120) --- p.66 === Chapter III.8.3.1. --- General feature of Palladium-catalyzed cross-coupling of aryl or vinyl halides with terminal alkynes (Stille-type reaction) --- p.66 === Chapter III.8.3.2. --- Palladium-catalyzed substitution of terminal alkynes with 4-iodo-3-(trimethylsilyl)furan (120): a convenient synthesis of 4-alkynyl-3-(trimethylsilyl)furan (127) --- p.67 === Chapter III.8.3.3. --- Mechanism --- p.69 === Chapter III.8.4 --- Palladium-catalyzed cross-coupling reaction of organoboronic acid with 4-iodo-3-(trimethylsilyl)furan (120) (Suzuki-type reaction) --- p.70 === Chapter III.8.4.1. --- General feature of Suzuki reaction --- p.70 === Chapter III.8.4.2. --- Suzuki-type reaction of 4-iodo-3-(trimethylsilyl)- furan (120) --- p.72 === Chapter III.8.5. --- Palladium- or nickel-catalyzed cross-coupling reaction of 4-iodo-3- (trimethylsilyl)furan (120) with bis(p-methoxycarbonyl)zinc and Grignard reagents --- p.73 === Chapter III.8.5.1. --- Palladium-catalyzed coupling of 4-iodo-3- (trimethylsilyl)furan (120) with bis(p- methoxycarbonyl)zinc --- p.73 === Chapter III.8.5.2. --- Nickel-catalyzed coupling of 4-iodo-3- (trimethylsilyl)furan (120) with Grignard reagents --- p.74 === Chapter III.9. --- "Regiospecific Conversion of 3,4-Bis(trimethyIsilyl)furan (105) to 3,4- Disubstituted Furans (147): A Novel Suzuki-Type Cross-Coupling of Boroxines" --- p.77 === Chapter III.9.1. --- General survey of boroxines --- p.77 === Chapter III.9.1.1. --- Introduction --- p.77 === Chapter III.9.1.2. --- Syntheses of boroxines --- p.78 === Chapter III.9.1.2.1. --- From boronic acid --- p.78 === Chapter III.9.1.2.2. --- From organolithium compounds --- p.78 === Chapter III.9.1.2.3. --- From trialkylborane --- p.79 === Chapter III.9.1.2.4. --- From trimethylborane and boric oxide --- p.80 === Chapter III.9.1.2.5. --- From dichloroborane --- p.81 === Chapter III.9.1.2.6. --- From carboxylic acid --- p.81 === Chapter III.9.1.3. --- The reactions of boroxines --- p.82 === Chapter III.9.1.3.1. --- Oxidation --- p.82 === Chapter III.9.1.3.2. --- Hydrolysis --- p.83 === Chapter III.9.1.3.3. --- Formation of complexes --- p.83 === Chapter III.9.1.3.4. --- Preparation of oxazaborolidine using trimethylboroxine --- p.85 === Chapter III.9.1.4. --- The structural feature of boroxines --- p.85 === Chapter III.9.2. --- Preparation and structural feature of tris[4-(trimethylsilyl)furan-3- yl]boroxine (144) --- p.87 === Chapter III.9.3. --- Palladium-catalyzed Suzuki-type cross-coupling reaction of tris[4- (trimethylsilyl)furan-3-yl]boroxine (144) --- p.89 === Chapter III.9.4. --- "Preparation and palladium-catalyzed Suzuki-type cross-coupling reactions of tris[4-(substituted)furan-3-yl]boroxines (145): Regiospecific synthesis of unsymmetrical 3,4-disubstituted furans (147)" --- p.93 === Chapter III.9.5. --- Mechanism of palladium-catalyzed Suzuki-type cross-coupling of boroxines --- p.98 === Chapter III.9.6. --- Iodination of boroxines --- p.99 === Chapter III. 10. --- "Regiospecific Synthesis of Furan-3,4-diyl Oligomers via Palladium- Catalyzed Self-Coupling of Boroxines" --- p.102 === Chapter III. 10.1. --- Palladium-catalyzed reactions of boroxines with ortho- bis(bromomethyl)arenes --- p.102 === Chapter III. 10.2. --- Reaction mechanism --- p.104 === Chapter III. 10.3. --- "Synthesis of furan-3,4-diyl oligomers" --- p.110 === Chapter III. 11. --- Conclusion --- p.116 === Experimental --- p.117 === References --- p.158 === Appendices === Chapter I. --- List of crystallographic data of tris[4-(trimethylsilyl)furan-3-yl]boroxine (144) --- p.172 === Chapter II. --- List of spectra --- p.177