Palladium-catalysed enantio- and regioselective (3 + 2) cycloaddition reactions of sulfamidate imine-derived 1-azadienes towards spirocyclic cyclopentanes.

An enantio- and diastereoselective Pd-catalysed (3 + 2) cycloaddition of bis(trifluoroethyl) 2-vinyl-cyclopropane-1,1-dicarboxylate (VCP) with cyclic sulfamidate imine-derived 1-azadienes (SDAs) has been developed. These reactions provide highly functionalized spiroheterocycles having three contiguous stereocentres, including a tetrasubstituted carbon bearing an oxygen functionality. The two geminal trifluoroethyl ester moieties can be manipulated in a facially selective manner to afford more diversely decorated spirocycles with four contiguous stereocentres. In addition, diastereoselective reduction of the imine moiety can also afford a fourth stereocentre and exposes the important 1,2-amino alcohol functionality.

The Pd-catalysed asymmetric allylic alkylation reactions of sulfamidate imines.

The Pd-catalysed asymmetric allylic alkylation (Pd-AAA) of prochiral enamide anions derived from 5H-oxathiazole 2,2-dioxides has been developed. Various 4,5-disubstituted and 4-substituted cyclic sulfamidate imines have participated in the transformation with a range of allyl carbonates-as well as 2-vinyl oxirane, 2-vinyl-N-tosylaziridine, and 2-vinyl-1,1-cyclopropane dicarboxylate-to furnish the desired C-allylated products in moderate to high yields, with high regioselectivites and generally high enantioselectivities. Conversion between N- and C-allyl products was observed, with the N-allylated products converting to the C-allylated products over time. The resulting high-value allylated heterocyclic products all bear a tetrasubstituted stereogenic centre and can be reduced to an allylated chiral sulfamidate or an amino alcohol.

Five-membered cyclic sulfamidate imines: versatile scaffolds for organic synthesis.

In recent years, five-membered ring cyclic sulfamidate imines (5H-1,2,3-oxathiazole 2,2-dioxides) have received increasing attention as useful precursors for the stereoselective synthesis of many valuable heterocycles. Bearing a reactive N-sulfonyl imine moiety as part of the stereodefined skeleton, this sulfamidate imine platform has been utilised as a substrate in many reactions, including nucleophilic additions and reductions, to prepare highly functionalised cyclic sulfamidates. In addition, cyclic sulfamidate imines can also readily participate as nucleophiles in many chemical transformations, owing to the acidic proton(s) adjacent to the imine moiety. This short review highlights recent developments involving cyclic sulfamidate imines, including their synthesis and reactivity, with a focus on stereoselective processes.