Organic Letters
Letter
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Scheme 4. One-Pot Reduction of Primary Amides to
Primary Amines
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reaction, and by finding a hydrosilane effective for both the
first and second reactions. However, these attempts have been
unsuccessful.
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Hydride Catalyst. Chem. Commun. 2017, 53, 7333−7336. (d) Weet-
In summary, a practical process was developed to convert
nitriles to primary amines with TMDS by cobalt carboxylate/
isocyanide catalyst systems. This process has great synthetic
utility, particularly the easy access to catalytically active species
from commercially available cobalt salts and isocyanides, and
use of inexpensive and easy-to-handle hydrosilane, TMDS. The
primary product is disilylamine 2, which is a good precursor to
primary amines and their HCl salts by hydrolysis, while
treatment of 2 with acyl chlorides provides easy access to
imides. The one-pot process involving Fe(OPiv)2-catalyzed
dehydration of primary amides with the HSiMe(OEt)2 and
Co(OPiv)2/CNR system catalyzed reduction of nitriles to
primary amines with TMDS furnishes the method for the
production of primary amines from primary amides.
̈
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Aromatic Nitriles to Primary Amines with Diisopropylaminoborane. J.
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ASSOCIATED CONTENT
* Supporting Information
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S
(5) For a review, see: Addis, D.; Das, S.; Junge, K.; Beller, M.
Selective Reduction of Carboxylic Acid Derivatives by Catalytic
Hydrosilylation. Angew. Chem., Int. Ed. 2011, 50, 6004−6011.
(6) (a) Huckaba, A. J.; Hollis, T. K.; Reilly, S. W. Homobimetallic
Rhodium NHC Complexes as Versatile Catalysts for Hydrosilylation
of a Multitude of Substrates in the Presence of Ambient Air.
Organometallics 2013, 32, 6248−6256. (b) Caporusso, A. M.;
Panziera, N.; Pertici, P.; Pitzalis, E.; Salvadori, P.; Vitulli, G.;
Martra, G. Hydrosilylation of Aromatic Nitriles Promoted by Solvated
Rhodium Atom-Derived Catalysts. J. Mol. Catal. A: Chem. 1999, 150,
275−285. (c) Campos, J.; Rubio, M.; Esqueda, A. C.; Carmona, E.
Large-scale Preparation and Labelling Reactions of Deuterated
Silanes. J. Labelled Compd. Radiopharm. 2012, 55, 29−38. (d) Corriu,
R. J. P.; Moreau, J. J. E.; Pataudsat, M. Reactions of ortho-
Bis(dimethylsilyl)benzene with Nitrile Catalyzed by Rhodium
Complexes. J. Organomet. Chem. 1982, 228, 301−308.
The Supporting Information is available free of charge on the
Experimental procedures, condition screening tables and
AUTHOR INFORMATION
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Corresponding Author
ORCID
Notes
(7) Gutsulyak, D. V.; Nikonov, G. I. Chemoselective Catalytic
Hydrosilylation of Nitriles. Angew. Chem., Int. Ed. 2010, 49, 7553−
7556.
The authors declare no competing financial interest.
(8) Cabrita, I.; Fernandes, A. C. A Novel Efficient and Chemo-
selective Method for the Reduction of Nitriles Using the System
Silane/oxo-Rhenium Complexes. Tetrahedron 2011, 67, 8183−8186.
(9) Hamdaoui, M.; Desrousseaux, C.; Habbita, H.; Djukic, J. P.
Iridacycles as Catalysts for the Autotandem Conversion of Nitriles
into Amines by Hydrosilylation: Experimental Investigation and
Scope. Organometallics 2017, 36, 4864−4882.
ACKNOWLEDGMENTS
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This work was supported by Grand-in-Aid for Scientific
Research (B) (No. 18H01980) from Japan Society for the
Promotion of Science. The authors are grateful to Ms. Yoshiko
Kusumori (Kyushu University) for experimental assistance.
REFERENCES
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Hydrosilylation of Nitriles Catalyzed by an Iron Complex Containing
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