Preparation of Allyl Sulfoxides by Palladium-Catalyzed Allylic Alkylation of Sulfenate Anions Guillaume Maitro, Guillaume Prestat, David Madec, ＊ and Giovanni.

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Presentation transcript:

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, 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