有机合成反应

1. 有机合成反应 唐 勇 金属有机化学国家重点实验室 2005.2 Shanghai, China

2. Chapter 4 The Chemistry of Nitrogen-based and related Compounds-1 Reading Assignment 1. Ho, T.-L. "Polarity Control for Synthesis"; John Wiley & Sons, Inc.: New York, 1991. 2. Ono, N., "The Nitro Group in Organic Synthesis", Wiley-VCH, 2001 Shanghai, China

3. § 4-1Some Reactions of Nitro Compounds Shanghai, China

4. p Problems of the day Shanghai, China

5. Shanghai, China

6. Reduction Shanghai, China

7. Nucleophilic Addition Shanghai, China

8. Electrophilic Substitution Seebach et. al. Tetrahedron Lett. 1977, 1161-1164 Shanghai, China

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10. Conjugate Addition Shanghai, China

11. McMurry et al. Chem Comm. 1971, 488-489. Bakuzis etal.Tetrahedron Lett.1978, 2371. Shanghai, China

12. –NO2 As a Leaving Group Review: Tamura et. al. Synthesis 1991, 423-434. Seebach, D. et al., Chimia, 1979, 33, 1-18 Shanghai, China

13. Other Reactions Shanghai, China

14. § 4-2 Reactions of Diazo Compounds Shanghai, China

15. Acid Catalyzed Reactions of Diazo Compounds • Review: Smith, et al. Tetrahedron 1981, 2407. Diazocarbonyl Diazonium Common acids include BF3•OEt2, HBF4, TFA, etc. Mechanism of activation is unclear for both Lewis and protic acids; activation may occur by protonation on C or O Shanghai, China

16. Mander, Chem. Comm. 1971, 773 & Tetrahedron, 1991, 134. Shanghai, China

17. Mander, JACS, 1980, 6626. Shanghai, China

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19. Polyene cyclizations: Smith, JACS, 1981, 2009. Mander, Aust. J. Chem. 1979, 1975. Shanghai, China

20. • Ring Expansion Reactions: Restriction: Starting ketone must be more reactive than product ketone Shanghai, China

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22. • Substitution Reactions Shanghai, China

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24. Reactions with Boranes Shanghai, China

25. Base-induced Reactions Shanghai, China

26. Carbene and Carbenoid Reactions: Decomposition can be catalyzed by: Heat or light Transition metals, including CuII, RhII, MnII, FeII, CoII, Ni0, NiII, ZnII, MoII, RuII, RuIII, PdII Most common catalysts: Copper (I): CuOTf, Cu(OTf)2, CuSO4, CuX, Cu(acac)2 Rhodium (II): Much milder catalyst than Cu (introduced in 1973 by Tessié); Structures generally contain bridging ligands and contain a Rh-Rh single bond; Reaction pathways are highly sensitive to steric and electronic effects. p p Shanghai, China

27. Precursors to Carbenes: p Shanghai, China

28. p Shanghai, China

29. Transition Metal Catalyzed Diazo Decomposition Doyle, Chem. Rev. 1986, 919. Shanghai, China

30. When X is a heteroatom, insertion is facile • When X is carbon: Only intramolecular processes • are generally useful • 5 - membered ring formation is favored in general • Order of selectivity: methine > methylene > methyl Shanghai, China

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42. Ylide Formation Shanghai, China

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46. Wolf Rearrangement Shanghai, China

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49. p Shanghai, China

50. § 4-3 Hydrazone-based Transformations • Wolff-Kischner Reduction • Wharton Rearrangement • Eschenmoser-Tanabe Fragmentation • Reduction of Tosyl Hydrazones: "The Alkene Walk“ • Tosyl Hydrazone-Based Fragment Coupling • The Shapiro Reaction • Bamford-Stevens Reaction Shanghai, China