Studies On The Application Of ?-fluoroamides In The Construction Of Chiral Carbon-fluorine Stereocenters

In this paper,the application of?-fluoro-substituted amides as fluorinated blocks in the construction of chiral C?sp³?-F bonds are introduced.A diastereoselective Mannich reaction has been developed for the construction of stereogenic C�F bonds by the reaction of?-fluoro-substituted amides,including highly activated 3-fluoro-oxindoles,and simple linear fluoroacetamides with N-tert-butylsulfinylimines.Under the condition of base?for example Li HMDS?,?-fluoroenolates and imide occured an addition reaction at-70?.The?-fluoro-?-amino amides containing fluorinated quaternary carbon chiral ceters were obtained in high diastereoselectivities and good yields.Further research of?-fluoro-substituted amides indicated the fluorinated?-carbon centers is stable under mild acidic or basic conditions.An Aldol reaction has been developed for the construction of stereogenic C�F bonds by the reaction of alphafluoro Thioester with aldehydes,Under the action of Mg Br₂�Et₂O/i Pr₂NEt,an addition reaction of?-fluoroenolates to aldehydes occured at room temperature.The?-fluoro-?-hydroxyl Thioester containing fluorinated carbon chiral centers were obtained.This paper provides a concise route to a variety of structurally diverse?-fluoro-?-amino amides and?-fluoro-?-hydroxyl thioester containing stereogenic fluorinated carbon centers.It is able to provide assistance for the synthesis of related fluoro-active molecules?...