Recent developments in the synthesis and utilization of chiral sulfoxides.

10. Patented Literature 2616 10.1. Esterification 2616 10.2. Ether Formation 2619 10.2.1. Etherification without Cyclization 2619 10.2.2. Etherification with Cyclization 2624 10.3. N-Alkylation 2625 10.4. Other Reactions 2627 11. Summary and Outlook 2628 12. Note Added in Proof 2628 13. Abbreviations Used in This Review 2629 14. Acknowledgments 2629 15. Supporting Information Available 2630 16. References 2630

Mitsunobu and Related Reactions: Advances and Applications

Sulfoxide ligation to Pd(II) salts is shown to selectively promote C-H oxidation versus Wacker oxidation chemistry and to control the regioselectivity in the C-H oxidation products. A catalytic method for the direct C-H oxidation of monosubstituted olefins to linear (E)-allylic acetates in high regio- and stereoselectivities and preparatively useful yields is described. The method using benzoquinone as the stoichiometric oxidant and 10 mol % of Pd(OAc)2 or Pd(O2CCF3)2 as the catalyst in a DMSO/AcOH (1:1) solution was found to be compatible with a wide range of functionality (e.g., amides, carbamates, esters, and ethers, see Table 2). Addition of DMSO was found to be critical for promoting the C-H oxidation pathway, with AcOH alone or in combination with a diverse range of dielectric media, leading to mixtures favoring Wacker-type oxidation products (Tables 1, S3). To explore the role of DMSO as a ligand, the bis-sulfoxide Pd(OAc)2 complex 1 was formed and found to be an effective C-H oxidation catalyst in the absence of DMSO (eqs 2, 3). Moreover, catalyst 1 effects a reversal of regioselectivity, favoring the formation of branched allylic acetates.

A sulfoxide-promoted, catalytic method for the regioselective synthesis of allylic acetates from monosubstituted olefins via C-H oxidation.

Further advances in the chemistry of mannich bases

Methods for the synthesis of gem-difluoromethylene compounds

Synthesis and Structural Investigations of Novel Palladium(II) and Rhodium(I) Complexes Containing Chiral Ligands with a Stereogenic Sulfur Donor, Such As β-Amino Sulfoxides and C2-Symmetric Bis-Sulfoxides1

Design, modelling, synthesis and biological evaluation of peptidomimetic phosphinates as inhibitors of matrix metalloproteinases MMP-2 and MMP-8.

High-performance liquid chromatographic procedure for the quantitation of norfloxacin in urine, serum and tissues

gem-Difluorocyclohexanols (7) and (16) bearing, respectively, the aryl- sulfinyl and the arylthio substituent are obtained by radical-promoted cyclization from the corresponding w-chlorodifluoroheptenols (6) and (9) in good yields. Intermediates (6) are made available by condensing the lithium derivative of chiral arylsulfinyl pentene (4) on ethyl chloro- difluoroacetate and by reducing the carbonyl with hydride-releasing agents. Elimination of the chiral auxiliary sulfinyl group and approp- riate elaborations afford enantiomerically pure α-hydroxy-, α-hydroxy- Δ3,4-, α,β,γ-trihydroxy-, and α-hydroxy-β,γ-epoxy-gem-difluorocyclohe- xane derivatives (19), (21), (22), and (23). Absolute and relative con- figurations as well as preferred conformations in solution are given. The defree of asymmetric induction during the radical-promoted cycliza- tion is correlated with the relative configuration of substituted carbons in open-chain compounds

Giancarlo Cavicchio

Papers

Synthesis and Structural Investigations of Novel Palladium(II) and Rhodium(I) Complexes Containing Chiral Ligands with a Stereogenic Sulfur Donor, Such As β-Amino Sulfoxides and C2-Symmetric Bis-Sulfoxides1

Design, modelling, synthesis and biological evaluation of peptidomimetic phosphinates as inhibitors of matrix metalloproteinases MMP-2 and MMP-8.

High-performance liquid chromatographic procedure for the quantitation of norfloxacin in urine, serum and tissues

Synthesis of Enantiomerically Pure gem-Difluorocyclohexane Derivatives by Intramolecular Trapping of .alpha.,.alpha.-Difluoroalkyl Radicals

New Efficient Synthetic Routes to Enantiomerically Pure Fluoroalkyl (Arylsulfinyl)methyl Imines and Amines