4. 取代反应解析.ppt

第4章 取代反应 1. Arbuzov (阿尔布佐夫) 反应 2. Gabriel 合成 3. Chichibabin 氨基化反应 4. Friedel-Crafts 反应 5. Sandmeyer 反应 6. Meerwein Arylation 反应 7. Reimer-Tiemann 反应 8. Grob 碎片化反应 9. Mitsunobu 反应 10. Stork 烯胺合成法 11. Hunsdiecker 反应 12. 其它取代 其它取代反应 Minisci Reaction Gattermann-Koch Reaction Wharton Fragmentation Williamson Ether Synthesis Others …… J. Org. Chem. 2003, 68, 8261-8263. Tetrahedron 2002, 58, 5979-5982. The architectural. novel macrolide (+)-zampanolide was synth. in the lab of A.B. Smith. The required PT-sulfone was prepared from the corresponding primary alcohol via a 2-step protocol employing sequential Mitsunobu reaction and S-S oxidation. Smith, A. B., III. et al. J. Am. Chem. Soc. 2001, 123, 12426-12427. A key Intermediate 实例1： A key Intermediate The total synth. of the bioactive indole alkaloid ent-WIN 64821 was accomplished by Overman et al. The stereospecific incorporation of two C-N bonds was achieved using ~ to convert two 2o alcohol functionalities to the corresponding alkyl azides with inversion of configuration. Overman, L. E., et al. J. Am. Chem. Soc. 2001, 123, 9465-9467. 实例2： ADDP: 偶氮二甲酰二哌啶 The nat. potent antitumor antibiotic (+)-duocarmycin A, its epimer, and unnat. enantiomers were prepar. by Boger et al. The last step was the elaboration of the reactive cyclopropane moiety, which was carried out via a transannular spirocyclization using ~. Boger, D. L. et al. J. Am. Chem. Soc. 1996, 118, 2301-2302. 实例3：▲▲▲ The total synth. of the tricyclic marine alkaloid (±)-fasicularin was firstly completed by Kibayashi et al. The 2o alcohol functionality was invert. using ~ protocol. Kibayashi, C. et al. J. Am. Chem. Soc. 2000, 122, 4583-4592. 实例4： Stork 烯胺合成法 The synthesis of α-alkyl- or acyl- carbonyl compounds via the alkylation or acylation of the corres. enamines is known as the Stork enamine synthesis 反应通式： 反应机理： The total synth. of the phenolic sesquiterpene (±)-parviflorine was accomplish. by Maldonado and co-workers. The key step in