Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines
Year: 2026
Type: preprint
Abstract: We disclose a highly regio- and enantioselective Ir(I)-catalyzed hydroamination of 1,1-disubstituted allenes, providing a broadly applicable access to α-tertiary chiral allylic amines, very relevant structural motifs that are mostly inaccessible through other enantioselective strategies. The method employs an a-aminopyridine as nucleophile, and displays a broad substrate scope, accommodating both aryl- and alkyl-substituted allenes. Removal of the pyridine moiety of the products yields synthetically challenging primary allylic amines bearing α-tetrasubstituted stereocenters. Notably, addition of i -PrOH after completion of the hydroamination enables an in situ transfer hydrogenation of the generated alkene to deliver the corresponding a-tertiary saturated amines with equally high selectivities. The use of trisubstituted allenes in the hydroamination protocol is also feasible, affording in this case a-secondary allylic amines, also with high selectivities. Finally, experimental and computational mechanistic studies support a hydrometalation/C–N bond-forming sequence as the preferred reaction pathway, with the C-N reductive elimination step identified as enantio- and TOF-determining.
Source: ChemRxiv
Language: English
Topic: Catalytic Alkyne Reactions
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7222743078