Hydrosilylation. hydrophosphonylation, and related reactions

A new family of Lewis basic 2-pyridyl oxazolines has been developed for Cl3SiH reduction of prochiral aromatic ketones and ketimines in CHCI3 with up to 94% ee and 89% ee, respectively.  

Hydroboration of aldehydes and ketones by pinacolborane is aided by a pre-catalyst cycle involving a heteroleptic magnesium alkyl complex and the ketone.  

Nucleophilic liuoroalkylations of a,/ -unsaturated carbonyl compounds with a-fluorinated sulfones have been shown to form 1,2- and 1,4-adducts under kinetic control in LiHMDS/THF. °5 

Conversion of aldehydes to terminal epoxides has been achieved with 95% ee, through methylene transfer from a chiral sulfonium ylid. °  

Umpolung behaviour has been achieved, whereby direct thioesterification of aldehydes (other than aliphatic) and enals by direct nucleophilic attack of carbonyl C on disulfides is promoted by an NHC and DBU/DEAD. °  

---