Current Organic Chemistry - Volume 8, Issue 2, 2004

This review deals with recent progress concerning the preparations, reactions, mechanisms and synthetic applications of some precursor compounds of the fluorine-containing reactive intermediates, such as phenyliodonium bis (perfluoro alkanesulfonyl) methides, PhI+--C(SO2Rf)2; perfluoroalkanesulfonyl azides, RfSO2N3 N,N-dichloro perfluoroalkanesulfonyl amides, RfSO2NCl2, aryldiazonium bis(perfluoro alkanesulfonyl) methides, ArN2 +--CH(SO2Rf)2, aryldiazonium bis(perfluoroalkanesulfonyl) imides, ArN2 +--N(SO2Rf)2 N-sulfinyl per- (or) polyfluoroalkanesulfonyl amides, RfSO2N=S=O, N-sulfinyl per- (or) polyfluorophenylaniline, ArFN=S=O. Under mild reaction conditions they react readily with many organic reagents to give various fluorine-containing products.

The oxidative activation of arenes is a powerful and versatile synthetic tactic that enables various functionalization of aromatic rings. Central to this chemistry are oxygenated arenes such as hydroxylated arenes or arenols and their simple alkyl ethers whose electron-releasing functions facilitate the oxidation process. These two classes of arenol derivatives can lead to three different types of oxidized intermediates, each of which expresses its own chemical reactivity that can be exploited for specific bond formation. Free arenols can be subjected to either one- or two-electron oxidation processes to furnish either neutral arenoxy ArO. radicals or arenoxenium ArO+ ions depending on the mode of oxidative activation used. Arenol ethers initially furnish radical cationic ArOR+. species, whose chemistry often expresses the duality of their electronic nature. This review highlights the chemical, biochemical and electrochemical oxidative activation modes that can be used to convert arenol derivatives into either ArO., ArO+ or ArOR+. species and focuses on the structural elaboration of these intermediates in selective carbon-carbon bond-forming reactions.

This review covers literature on enantioselective synthesis of molecules with substituted quaternary carbon stereocenters from 1992 to 2002. In this overview, we will consider not only the construction of stereocenter itself by generation of carbon-carbon bond or heteroatom-carbon bond, but also other approachs which deal with the preparation of chiral compounds having this type of stereocenters, such as resolution or enantioselective desymmetrization.

Synthetic studies on the specific inhibitors of vacuolar-type H+-ATPase, bafilomycins, hygrolidines, and concanamycins, are described. Bafilomycins and hygrolidins are 16-membered and concanamycins are 18- membered plecomacrolides, which have very complex molecular structures.