10.1002/cctc.201601155
ChemCatChem
COMMUNICATION
General
procedure for
the
one-pot
oxidation/1,3-dipolar
Donck, E. Gravel, N. Shah, D. V. Jawale, E. Doris, I. N. N. Namboothiri,
ChemCatChem 2015, 7, 2318.
cycloaddition of nitrones with alkynes
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N. Namboothiri, E. Doris, Chem. Commun. 2015, 51, 1739; (b) P. Basu,
P. Prakash, E. Gravel, N. Shah, K. Bera, E. Doris, I. N. N. Namboothiri,
ChemCatChem 2016, 8, 1298.
Path A conditions: to a solution of N,N-dibenzyl hydroxylamine 1a (10.7
mg, 0.05 mmol) in methanol (2 mL), was added RhCNT (6.4 mM
methanol suspension, 1 mol%) and the reaction mixture was stirred at
room temperature. After the disappearance of hydroxylamine (monitored
by TLC), the alkyne (0.05 mmol) was added and the reaction mixture was
stirred for the corresponding time. The catalyst was removed by filtration
and methanol was removed under vacuum. The residue was subjected to
column chromatography (silica gel, cyclohexane/ethyl acetate) to afford
the cycloadduct.
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Namboothiri, E. Doris, Chem. Eur. J. 2015, 21, 7039; (b) S. Donck, E.
Gravel, A. Li, P. Prakash, N. Shah, J. Leroy, H. Li, I. N. N. Namboothiri,
E. Doris, Catal. Sci. Technol. 2015, 5, 4542.
[13] (a) A. Morozan, S. Donck, V. Artero, E. Gravel, E. Doris, Nanoscale
2015, 7, 17274 ; (b) T. N. Huan, P. Prakash, P. Simon, G. Rousse, X.
Xiangzhen, V. Artero, E. Gravel, E. Doris, M. Fontecave,
ChemSusChem 2016, DOI : cssc.201600597
Path B conditions: N,N-dibenzyl hydroxylamine 1a (10.7 mg, 0.05 mmol),
hydroquinone (0.5 mg, 0.005 mmol) and RhCNT (6.4 mM methanol
suspension, 1 mol%) were stirred in methanol at room temperature for
1.2 h. After the disappearance of hydroxylamine (monitored by TLC), the
alkyne (0.05 mmol) was added and the reaction mixture was stirred for
the corresponding time. The catalyst was removed by filtration and
methanol was removed under vacuum. The residue was subjected to
column chromatography (silica gel, cyclohexane/ethyl acetate) to afford
the cycloadduct.
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Namboothiri, E. Doris, Chem. Commun. 2014, 50, 15251.
[16] Disubstituted hydroxylamines were synthesized according to previously
reported procedures: (a) R. F. Borch, M. D. Bernstein, H. D. Durst, J.
Am. Chem. Soc. 1971, 93, 2897; (b) I. A. O’Neil, E. Cleator, D. J.
Tapolczay, Tetrahedron Lett. 2001, 42, 8247; (c) C. Gella, E. Ferrer, Ra.
Alibés, F. Busqué, P. de March, M. Figueredo, J. Font, J. Org. Chem.
2009, 74, 6365.
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Ouattara, A. T. Pezacki, J. P. Pezacki, Bioconjugate Chem. 2016, 27,
1222.
Acknowledgements
Supports from the Indo-French Centre for the Promotion of
Advanced Research (IFCPAR)/Centre Franco-Indien pour la
Promotion de la Recherche Avancée (CEFIPRA) (Project no.
4705-1) and the Enhanced Eurotalent program are gratefully
acknowledged. The TEM-team platform (CEA, iBiTec-S) is
acknowledged for help with TEM images. The “Service de
Chimie Bioorganique et de Marquage” belongs to the Laboratory
of Excellence in Research on Medication and Innovative
Therapeutics (ANR-10-LABX-0033-LERMIT).
Keywords: carbon nanotubes • heterogeneous catalysis •
hydroxylamines • nitrones • rhodium nanoparticles
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