Total asymmetric synthesis of glycomimetics and polypropionates of biological interest
Using readily available chiral auxiliaries such as (+)- and (-)-camphanic acid, (R,R)- and (S,S)-tartaric acid derivatives (e.g. RADO(R)-COCl, SADO(R)-COCl) efficient diastereoselective syntheses of rare sugars and glycomimetics have been developed. They engage the 'naked sugar' (enantiomerically pure 7-oxanorbornene) methodologies in which the chiral auxiliaries are recovered at an early stage of the multistep syntheses. A new reaction cascade starting with the hetero-Diels-Alder addition of sulfur dioxide to 1-(1-phenylethoxy)-1,3-dienes derived from inexpensive (+)- and (-)-1-phenylethanol allows the one-pot, four-component synthesis of polyfunctional sulfones, sulfonamides and sulfonic esters containing up to three stereogenic centers. The method ensures a high molecular and stereochemical diversity. The reaction cascade can also produce polyketide and polypropionate fragments in one-pot operations. The latter contain up to three contiguous stereogenic centers and do not have to be modified (deprotection, activation) before using them as nucleophilic partners in diastereoselective cross-aldol reactions, thus permitting the quick access to complicated polypropionate antibiotics such as Baconipyrones, Ryfamicyn S and Apoptolidines.
Keywords: chiral auxiliaries ; diastereoselective synthesis ; 'naked sugars' ; new organic chemistry of sulfur dioxide ; polypropionate antibiotics ; Derivatives Naked Sugars ; Bond-Forming Reaction ; Diels-Alder Adducts ; Mediated One-Pot ; Sulfur-Dioxide ; Enantiomerically Pure ; 4-Component Synthesis ; Stereoselective-Synthesis ; Polyfunctional Sulfones ; Organic-Chemistry
Record created on 2010-11-30, modified on 2016-08-09