Synthesis of 3,4-disubstituted furans and 3-substituted furans using 3,4-bis(tri-n-butylstannyl)furan and 3-(tri-n-butylstainnyl)furan as building blocks.

• Other Authors: Yang, Yün.
• Format: Others
• Language: English
• Published: Chinese University of Hong Kong 1993
• Subjects: Furans; Diels-Alder reaction
• Online Access: http://library.cuhk.edu.hk/record=b5895763; http://repository.lib.cuhk.edu.hk/en/item/cuhk-319116

by Yun Yang. === Thesis (Ph.D.)--Chinese University of Hong Kong, 1993. === Includes bibliographical references (leaves 111-118). === Acknowledgements --- p.i === Contents --- p.ii === Abstract --- p.v === List of Acronyms and Abbreviations --- p.vi === Chapter Chapter 1. --- Introduction === Chapter 1.1 --- Background --- p.1 === Chapter 1.2 --- Reactions of Furans === Chapter 1.2.1 --- Electrophilic Substitution --- p.3 === Chapter 1.2.2 --- Nucleophilic Substitution --- p.6 === Chapter 1.2.3 --- Addition Reaction --- p.9 === Chapter 1.2.4 --- Oxidation Reaction --- p.9 === Chapter 1.3 --- Review of Synthetic Methods for the Syntheses of Polysubstitued Furans --- p.11 === Chapter 1.3.1 --- "From 1,4-Dicarbonyl Compounds" --- p.11 === Chapter 1.3.2 --- From α-Haloketones --- p.12 === Chapter 1.3.3 --- From Hetero Diels-Alder and Retro-Diels-Alder Reactions --- p.15 === Chapter 1.3.4 --- From Alkynes === Chapter 1.3.4.1 --- Via Radical Cyclization --- p.16 === Chapter 1.3.4.2 --- Via Insertion of Isocyanides --- p.16 === Chapter 1.3.4.3 --- Via Addition of Carbenoids --- p.17 === Chapter 1.3.4.4 --- Via Pd-Catalyzed Addition and Cyclization Reactions --- p.19 === Chapter 1.3.5 --- FromAllenes === Chapter 1.3.5.1 --- Via Allenic Sulfonium Salts --- p.20 === Chapter 1.3.5.2 --- Via Rh or Ag Catalyzed Cyclization --- p.21 === Chapter 1.3.5.3 --- Via Acylium Ions Addition to Allenylsilanes --- p.21 === Chapter 1.3.5.4 --- Via Allenic Palladium Intermediates --- p.22 === Chapter 1.3.6 --- From Pyrylium Salts --- p.23 === Chapter 1.3.7 --- From Miscellaneous Sources --- p.24 === Chapter 1.4 --- "Review of Synthetic Methods for the Syntheses of 3,4-Disubstituted Furans" === Chapter 1.4.1 --- From Functionalization of Furan Ring --- p.25 === Chapter 1.4.1.1 --- "Modification of Diethyl Furan-3,4-dicarboxylate" --- p.25 === Chapter 1.4.1.2 --- Modification of 3-(Hydroxymethyl)furan --- p.27 === Chapter 1.4.1.3 --- "From Boroxines Derived from 3,4-Bis(trimethylsilyl)furan…" --- p.28 === Chapter 1.4.2 --- From Ylide --- p.29 === Chapter 1.4.3 --- "From 2-Butyne-l,4-diol" --- p.29 === Chapter 1.4.4 --- From Hetero Diels-Alder and Retro-Diels-Alder Reactions --- p.30 === Chapter 1.4.5 --- From Sulfolene --- p.31 === Chapter 1.5 --- Aim of the Present Work --- p.32 === Chapter Chapter 2. --- Results and Discussion === Chapter 2.1 --- "Synthesis of 3,4-Bis(tri-n-butylstannyl)furan (47) and 3-(Tri-n-butylstannyl)furan (48) from Bis(tri-n-butylstannyl)acetylene (49) and 4-Phenyloxazole (50)" --- p.34 === Chapter 2.2 --- Stille-type Palladium-catalyzed Cross-coupling Reactions with Various Organic Halides --- p.36 === Chapter 2.2.1 --- General Features of Stille's Reaction --- p.38 === Chapter 2.2.2 --- Solvents and Catalysts --- p.42 === Chapter 2.2.3 --- Isolation and Purification of Products --- p.45 === Chapter 2.2.4 --- Direct Coupling with Organic Halides --- p.45 === Chapter 2.2.4.1 --- Acid Chloride --- p.46 === Chapter 2.2.4.2 --- Aryl Halide --- p.51 === Chapter 2.2.4.3 --- Vinyl Halide --- p.53 === Chapter 2.2.4.4 --- Allylic Bromide --- p.53 === Chapter 2.2.4.5 --- Benzylic Halide --- p.54 === Chapter 2.2.5 --- Mechanistic Aspects === Chapter 2.2.5.1 --- Mechanism for the Stille's Reaction of Acid Chloride --- p.54 === Chapter 2.2.5.2 --- Mechanism for the Stille's Reaction of Aryl Halide --- p.56 === Chapter 2.2.6 --- Carbonylative Coupling --- p.59 === Chapter 2.2.7 --- Conclusion --- p.64 === Chapter 2.3 --- "Synthesis of Unsymmetrical 3,4-Disubstituted Furans via Lithiation of 3,4-Bis(tri-n-butylstannyl)furan (47)" === Chapter 2.3.1 --- Lithiation of Organotin Compounds: General Remarks --- p.65 === Chapter 2.3.2 --- "Lithiation of 3,4-Bis(tri-n-butylstannyl)furan (47) with n-BuLi" --- p.68 === Chapter 2.3.3 --- Trapping of 3-Lithium-4-(tri-n-butylstannyl)furan (63) with Electrophiles --- p.70 === Chapter 2.3.4 --- "Synthesis of Unsymmetrical 3,4-Disubstituted Furans from 3-Substituted-4-(tri-n-butylstannyl)furan (64) via Stille's Reactions" --- p.72 === Chapter 2.3.5 --- Conclusion --- p.75 === Chapter 2.4 --- Halogenation --- p.75 === Chapter Chapter 3. --- Application to Natural Product Synthesis === Chapter 3.1 --- "Synthesis of a Key Intermediate in the Total Synthesis of (20,S)-Camptothecin" --- p.79 === Chapter 3.2 --- Synthesis of an Analog of Lactaral --- p.80 === Experimental --- p.83 === References --- p.111 === Appendix --- p.119