1. Preparation of Allyl Sulfoxides by Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions Guillaume Maitro, Guillaume Prestat, David Madec, ＊ and Giovanni Poli ＊ J. Org. Chem. 2006, 71, 7449-7454 演講者：化生四 張永宏

2. 2 Allyl Sulfoxides Allyl sulfoxides are versatile and valuable building blocks in organic synthesis. It is proved by their use in the preparation of various functionalized compounds and natural products.

3. 3 Palladium-Catalyzed Allylic Alkylation of Sulfur Nucleophiles

4. 4 Generations of Carbon-Heteroatom Bonds by Palladium Complex

5. 5 Synthesis of Allyl Sulfoxides

6. 6 Mechanism of The Synthesis of Sulfenate

7. 7 Methods of Generation of Sulfenate Anions Sulfur oxidation Addition-elimination reaction Ring-opening reaction Ring manipulation route Sigmatropic rearrangement Metal insertion reaction Retro-Michael reaction

8. 8 Generation of Sulfenate Anions by Sulfur Oxidation Sulfenate anions are of limited stability. A competitive oxidative pathway leading to symmetrical disulfides may occur. The oxidizing agents employed up to now, m-CPBA and hydrogen peroxide, were not particularly well suited to this task.

9. 9 Generation of Sulfenate Anions by Metal Insertion Reaction

10. 10 Generation of Sulfenate Anions by Ring-Opening Reaction

11. 11 Methods of Generation of Sulfenate Anions Sulfur oxidation Addition-elimination reaction Ring-opening reaction Ring manipulation route Sigmatropic rearrangement Metal insertion reaction Retro-Michael reaction

12. 12 Generation of Sulfenate Anions by retro- Michael reaction

13. 13 The Catalytic Cycle for Transition Metal-Catalyzed Allylic Alkylations

14. 14 Preparation of β-Sulfinylesters

15. 15 Mechanism of The Preparation of The β-Sulfinylesters

16. 16 Mechanism of The Formation of Sulfenate Anions

17. 17 Optimization of Reaction Conditions

18. 18 Allylic Acetates

19. 19 Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

20. 20 The Interconversion Equilibrium between The Two Diastereomers

21. 21 Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

22. 22 Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

23. 23 Allylic Alkylations in Biphasic Conditions

24. 24 Conclusions  We have reported the first palladium-catalyzed allylation of sulfenate anions.  This new, smooth, and operationally very simple method further extends the set of sulfur-based nucleophiles that can be successfully allylated under palladium catalysis.  The stereogenic nature of the sulfur atom in the generated allyl sulfoxides, and the potential sulfoxide-sulfenate rearrangement associated to these compounds are expected to make of this reaction a synthetically interesting transformation.

25. 25 n-BuLi/(-)-sparteine