Concerning the Phosphorylation of Vicinal Diols

Synthesis of a Lipomannan Component of the Cell‐Wall Complex ofMycobacterium tuberculosisIs Based on Paulsen's Concept of Donor/Acceptor “Match”

“…Palladium-catalyzed deallylation provided 13 (Scheme 4), and the resulting inositol-1-OH cooperated well with our standard phosphoglycero-lipidation protocol [23] involving reaction with the lipidated glyceryl phosphoramidite followed by oxidation with MCPBA.…”

A Catalytic and Enantioselective Desymmetrization of meso Cyclic Allylic Bisdiethylphosphates with Organozinc Reagents

“…Herein we present a new highly regio‐, diastereo‐, and enantioselective desymmetrization of meso, cyclic allylic bisdiethylphosphates with organozinc reagents3 catalyzed by copper( I ) complexes of chiral Schiff base ligands 1 4 . cis ‐4‐Cyclopentene‐1,3‐diol was transformed into the corresponding bisdiethylphosphate 2 by deprotonation with n BuLi and reaction with diethylchlorophosphate in THF/TMEDA (4:1) 5. Reaction of meso ‐4‐cyclopentene‐1,3‐bisdiethylphosphate ( 2 ) with diethylzinc in the presence of (CuOTf) 2 ⋅C 6 H 6 (Tf=CF 3 SO 2 ) (10 mol %) and chiral ligand 1 cjl in toluene/THF (95:5 v/v) at −78 °C afforded only the product arising from the S N 2′ mechanism with inversion of stereochemistry, with an enantiomeric ratio 3 / 4 of 87:13 in favor of the S,S enantiomer (Scheme ) 6–8.…”

A Catalytic and Enantioselective Desymmetrization of meso Cyclic Allylic Bisdiethylphosphates with Organozinc Reagents

“…Herein we present a new highly regio‐, diastereo‐, and enantioselective desymmetrization of meso, cyclic allylic bisdiethylphosphates with organozinc reagents3 catalyzed by copper( I ) complexes of chiral Schiff base ligands 1 4 . cis ‐4‐Cyclopentene‐1,3‐diol was transformed into the corresponding bisdiethylphosphate 2 by deprotonation with n BuLi and reaction with diethylchlorophosphate in THF/TMEDA (4:1) 5. Reaction of meso ‐4‐cyclopentene‐1,3‐bisdiethylphosphate ( 2 ) with diethylzinc in the presence of (CuOTf) 2 ⋅C 6 H 6 (Tf=CF 3 SO 2 ) (10 mol %) and chiral ligand 1 cjl in toluene/THF (95:5 v/v) at −78 °C afforded only the product arising from the S N 2′ mechanism with inversion of stereochemistry, with an enantiomeric ratio 3 / 4 of 87:13 in favor of the S,S enantiomer (Scheme ) 6–8.…”