Stereoselective\nConstruction of Less-Accessible Acyclic\nQuaternary Carbon Stereocenters via Rhodium-Catalyzed Allylic Alkylation\nof β,β-Disubstituted Enesulfinamides

In the presence of Wilkinson’s catalyst, the <i>N</i>-sulfinyl metalloenamines derived from NH-deprotonation\nof β,β-disubstituted\nenesulfinamides undergo nucleophilic allylic substitution with allyl\ncarbonate, affording α-allylated ketimines with high stereoselectivity.\nThese allylation products possess challenging acyclic quaternary stereocenters\ncontaining one allyl group and two alkyl groups that are both sterically\nand electronically similar (<i>e.g</i>., Me and Et). By\nutilizing appropriate stereoisomers of enesulfinamides, it becomes\nfeasible to selectively access each of the four potential stereoisomers\nof the allylation products, thereby facilitating the selective synthesis\nof stereoisomers of α-tertiary chiral amines featuring a β-quaternary\nstereocenter through imino nucleophilic addition.