Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines
- 1Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departa-mento de Química Orgánica.
- 2Universidade de Santiago de Compostela
- 3Misión Biológica de Galicia (MBG), Consejo Superior de Investigaciones Científicas (CSIC)
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.
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BibTeX
@misc{rey2026iridiumcatalyzed,
title = {{Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines}},
author = {Alejandro Rey and María Puente and José L Mascareñas and Fernando López},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.10001679/v4},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.10001679/v4},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Iridium-Catalyzed Regio- and Enantioselective Hydroamination of Allenes: Direct Access to α-Tertiary Chiral Allylic Amines
AU - Alejandro Rey
AU - María Puente
AU - José L Mascareñas
AU - Fernando López
PY - 2026
DA - 2026/10/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.10001679/v4
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.10001679/v4
AB - 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.
ER -