Optically Pure Polyfluoroalkanesulfinamides: Synthesis and Application as Promising and Monitorable Chiral Auxiliaries

Abstract

Efficient synthesis of enantiopure polyfluoroalkanesulfinamides (PFSAs) has been achieved. Their application as novel chiral auxiliaries with an electron-withdrawing and (19)F NMR monitorable polyfluoroalkyl group was initially demonstrated in an asymmetric Strecker reaction under mild conditions.

Synthesis of Chiral β‐Aminomalonates from 2‐Chlorotetrafluoroethanesulfinyl Aldimines through the Mannich Reaction

“…Procedure for the Synthesis of Racemic and ( S )‐2‐Chlorotetrafluoroethanesulfinamide 9a : 2‐Chlorotetrafluoroethanesulfinyl chloride (0.075 mol) was added dropwise at 0 °C to a flask containing neat hexamethyldisilazane (HMDS, 0.075 mol). After addition, stirring was continued for 2 h at room temperature.…”

A Chiral Sulfoxide-Based C–H Acid

“…The title compound was prepared using a literature procedure. 2 A Schlenk flask was charged with (R)-(-)-4-phenyl-2-oxazolidinone (1.3 g, 8.0 mmol, 1.0 equiv). THF (48 mL) was added and a clear, colorless solution was obtained, to which n-BuLi (3.7 mL, 2.4 M sol.…”

One-pot asymmetric reductive amination of ketones induced by polyfluoroalkanesulfinamide

“…Recently, our group developed a novel fluorinated chiral auxiliary, polyfluoroalkanesulfinamide, which was applied successfully in many asymmetric reactions such as Strecker reaction, [12] three component aza Diels-Alder reaction [13] , aminoallylation of aldehydes [14] and asymmetric vinylogous Mannich reaction. [15] Using this kind of fluorinated auxiliary, Ellman's group also developed an asymmetric intermolecular addition of non-acidic C-H bonds for the first time.…”