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Preparation of Allyl Sulfoxides by Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

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. Allyl Sulfoxides.

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Preparation of Allyl Sulfoxides by Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

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  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. 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. Palladium-Catalyzed Allylic Alkylation of Sulfur Nucleophiles

  4. Generations of Carbon-Heteroatom Bonds by Palladium Complex

  5. Synthesis of Allyl Sulfoxides

  6. Mechanism of The Synthesis of Sulfenate

  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. 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. Generation of Sulfenate Anions by Metal Insertion Reaction

  10. Generation of Sulfenate Anions by Ring-Opening Reaction

  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. Generation of Sulfenate Anions by retro-Michael reaction

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

  14. Preparation of β-Sulfinylesters

  15. Mechanism of The Preparation of The β-Sulfinylesters

  16. Mechanism of The Formation of Sulfenate Anions

  17. Optimization of Reaction Conditions

  18. Allylic Acetates

  19. Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

  20. The Interconversion Equilibrium between The Two Diastereomers

  21. Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

  22. Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions

  23. Allylic Alkylations in Biphasic Conditions

  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. n-BuLi/(-)-sparteine

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