Hydrogenolysis of N-Cbz-Protected Amines Mediated by Spherical SiliaCat Pd(0)
- 1Zeochem Silica Materials, 2500 Boulevard du Parc Technologique, Québec, QC, Canada, G1P 4S6
- 2Istituto per lo Studio dei Materiali Nanostrutturati, CNR, via U. La Malfa 153, Palermo, Italy, 90146
Abstract
The deprotection reaction of N-benzyloxycarbonyl (N-Cbz)-protected amino groups in organic compounds can be efficiently achieved by hydrogenolysis mediated by the sol-gel-entrapped spherical catalyst SiliaCat Pd(0). The heterogeneous catalyst combines high catalytic activity and chemoselectivity with low Pd loading, a nonpyrophoric nature, and excellent reusability. Investigation of the effects of solvent, substrate concentration, Pd loading, temperature, and catalyst particle size revealed that 100 µm spherical SiliaCat Pd(0) provides a favorable balance between rapid reaction kinetics and practical catalyst properties for batch applications. The catalyst was successfully reused over ten consecutive reaction runs, maintaining complete conversion and high isolated yields. A broad substrate scope was demonstrated, with tolerance toward methyl esters, Boc-protected amines, pinacol boronate esters, and an aliphatic bromide, while debromination of an aryl bromide revealed a limitation of the method. Comparison of the 100 µm spherical sol-gel catalyst with several commercial heterogeneous Pd catalysts demonstrates its high catalytic activity and selectivity under mild reaction conditions.
Related
- Direct Access to α-Aryl-β-Amino Aldehydes via Hypervalent Iodine-Mediated Oxidative Rearrangement of Cinnamyl Amines
- Enantio-Complementary Synthesis of Atropisomeric C–N Biaryl Amines via Imine Reductase-Mediated Dynamic Kinetic Resolution
- Alkali hydrides catalyze hydrogenolysis of polystyrene to alkylbenzenes under mild conditions
- Methylcyclohexane-assisted polypropylene upcycling over PtRu/Al₂O₃ via tandem dehydrogenation-hydrogenolysis.
- Hydrogenolysis triggered formation of zero-valent metals and metal selenides at room temperature from divalent metal aminoxide complexes facilitated by metal-ligand cooperativity
BibTeX
@misc{pandarus2026hydrogenolysis,
title = {{Hydrogenolysis of N-Cbz-Protected Amines Mediated by Spherical SiliaCat Pd(0)}},
author = {Valerica Pandarus and Samuel Cashman-Kadri and Rosaria Ciriminna and François Béland and Mario Pagliaro},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010161/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010161/v1},
note = {CC BY-NC},
}
RIS
TY - UNPB
TI - Hydrogenolysis of N-Cbz-Protected Amines Mediated by Spherical SiliaCat Pd(0)
AU - Valerica Pandarus
AU - Samuel Cashman-Kadri
AU - Rosaria Ciriminna
AU - François Béland
AU - Mario Pagliaro
PY - 2026
DA - 2026/10/09
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010161/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010161/v1
AB - The deprotection reaction of N-benzyloxycarbonyl (N-Cbz)-protected amino groups in organic compounds can be efficiently achieved by hydrogenolysis mediated by the sol-gel-entrapped spherical catalyst SiliaCat Pd(0). The heterogeneous catalyst combines high catalytic activity and chemoselectivity with low Pd loading, a nonpyrophoric nature, and excellent reusability. Investigation of the effects of solvent, substrate concentration, Pd loading, temperature, and catalyst particle size revealed that 100 µm spherical SiliaCat Pd(0) provides a favorable balance between rapid reaction kinetics and practical catalyst properties for batch applications. The catalyst was successfully reused over ten consecutive reaction runs, maintaining complete conversion and high isolated yields. A broad substrate scope was demonstrated, with tolerance toward methyl esters, Boc-protected amines, pinacol boronate esters, and an aliphatic bromide, while debromination of an aryl bromide revealed a limitation of the method. Comparison of the 100 µm spherical sol-gel catalyst with several commercial heterogeneous Pd catalysts demonstrates its high catalytic activity and selectivity under mild reaction conditions.
ER -