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into the corresponding nitriles which were then reduced into the
corresponding amines in high selectivity and excellent yields.
9. (a) Hanada, S.; Motoyama, Y.; Nagashima, H. Eur. J. Org. Chem. 2008, 4097–
4100; (b) Zhou, S.; Junge, K.; Addis, D.; Das, S.; Beller, M. Org. Lett. 2009, 11,
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2009, 4883–4885.
10. Safety alerts have been published concerning hazards and risks of hydrosilanes
related to the unexpected generation of silane, SiH4, an extremely dangerous,
toxic, pyrophoric and explosive gas. See: (a) Berk, S. C.; Buchwald, S. L. J. Org.
Chem. 1992, 57, 3751–3753. and J. Org. Chem. 1993, 58, 3221; (b) Wells, A. S.
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Acknowledgments
This work was financially supported by the ‘Fond Unique Inter-
ministériel’ (FUI). The authors are grateful for the access to MS and
NMR facilities at the Université de Lyon 1—La Doua—France.
References and notes
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higher temperature, TMDS risks to get evaporated out of the reaction medium.
13. Polymethylhydrosiloxane (PMHS, n = 40) and titanium(IV) isopropoxide 95%
were purchased from Alfa Aesar; extra dry toluene from Acros Organics;
primary amides from Alfa Aesar, Acros Organics, Maybridge, and sigma Aldrich.
All reagents, reactants and solvents were used in the state without further
purification.
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& Sons Inc, 2010. by Organic Reactions and the
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14. General procedure for the reduction of primary amides into amines: 2-
(trifluoromethyl)-benzamide 1a. To
containing 1a (250 mg, 1.3 mmol, 1.0 equiv) and 2.0 ml of anhydrous toluene
were added PMHS (320 l, 5.4 mmol, 4.2 equiv) and Ti(OiPr)4 (400 l,
a nitrogene purged screw-cap vial
l
l
1.3 mmol, 1.0 equiv) at rt. The mixture was stirred and heated at 100 °C until
analysis by tlc showed complete consumption of the starting material (ca.
overnight). The mixture was then diluted with Et2O (30.0 ml) and acidified
using 2 M Et2O–HCl solution (2.0 ml, 3.0 equiv). The ammonium salt 4a was
precipitated, filtered, and washed first with Et2O and then with pentane. The
primary amine 4a was isolated as the hydrochloride salt in 89% yield.
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