The Journal of Organic Chemistry
Note
S.; Dittrich, B.; Meyer, J.; Maity, B.; Koley, D.; Schwederski, B.; Kaim,
W.; Roesky, H. W. J. Am. Chem. Soc. 2015, 137, 4670.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
(12) Belzner, J.; Dehnert, U.; Ihmels, H.; Hubner, M.; Muller, P.;
̈
̈
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Usοn, I. Chem. - Eur. J. 1998, 4, 852.
(13) Meyer-Wegner, F.; Nadj, A.; Bolte, M.; Auner, N.; Wagner, M.;
Holthausen, M. C.; Lerner, H.-W. Chem. - Eur. J. 2011, 17, 4715.
(14) A further evidence of the importance of the amine molecule in
the reduction process comes from our optimized protocol that
typically requires 5 mol/equiv of base for 3 mol/equiv of HSiCl3,
where 1 equiv is used to deprotonate trichlorosilane and the excess
may be hypothesized to stabilize the resulting reducing species. For the
ability of amines to stabilize SiCl2, see refs 13 and 11.
Spectroscopic data for the reduction of compound 1,
HSAB theory details, NMR spectra for SiCl2 generation
methods from other sources, Table S3 for competition
experiments, in silico competition experiments, and
geometries of TSs A−D (PDF)
(15) (a) Uhlig, F.; Marsmann, H. C. In 29Si NMR, Some Practical
Aspects, from Gelest Catalog: Silicon Compounds, Silanes & Silicones, 2nd
ed.; Arkles, B.; Larson, G., Eds.; Gelest Inc.: Morrisville, PA, 2008; pp
AUTHOR INFORMATION
Corresponding Author
Notes
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A.; Buffy, J. J.; Powell, D. R.; West, R.; Muller, T. Chem. Ber. 1997,
̈
130, 1579.
The authors declare no competing financial interest.
(16) The TSs were calculated with the B3LYP, M06-2X, and
wB97XD functionals using the 6-311++G(3df,3pd) basis set and PCM
model for the inclusion of chloroform as the solvent (the same used
also in the NMR experiments). Finer single point energy values have
also been calculated at the post-Hartree−Fock MP2/6-311+G(2d,2p)
level of theory.
ACKNOWLEDGMENTS
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M.B. thanks Universita
SpA (Zambon Chemicals); M.O. thanks Universita
di Milano for a Ph.D. fellowship.
̀
degli Studi di Milano and ZaCh System
̀
degli Studi
(17) (a) Anslyn, E. V.; Dougherty, D. A. In Modern Physical Organic
Chemistry; University Science Books: Herndon, VA, 2006. (b) Hansh,
C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
REFERENCES
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(1) Orlandi, M.; Tosi, F.; Bonsignore, M.; Benaglia, M. Org. Lett.
2015, 17, 3941 The methodology is described in a patent:
International Patent Application: Bonsignore, M.; Benaglia, M.
(18) It is worth mentioning that, by monitoring the reaction via 29Si
NMR, some peaks at ca. −45, −55, and −65 ppm have been detected,
typical of species which present Si atoms directly bound to one, two,
or three O and/or N and Cl atoms. See ref 15.
̀
PCT/EP/2013/0683 (Universita degli Studi di Milano, Milano,
Italy), now owned by DexLeChem GmbH (Berlin, Germany)..
(2) (a) Downing, R. S.; Kunkeler, P. J.; van Bekkum, H. Catal. Today
1997, 37, 121. (b) Ono, N., Ed. The Nitro Group in Organic Synthesis;
Wiley-VCH: New York, 2001. (c) For a review on selective
hydrogenation of nitroarenes, see: Blaser, H. U.; Steiner, H.; Studer,
M. ChemCatChem 2009, 1, 210.
(19) (a) King, F. D.; Caddick, S. Tetrahedron 2013, 69, 8592.
(b) Reddy, M. M.; Kumar, M. A.; Swamy, P.; Naresh, M.; Srujana, K.;
Satyanarayana, L.; Venugopal, A.; Narender, N. Green Chem. 2013, 15,
3474.
(20) Kumar, D.; Sonawane, M.; Pujala, B.; Jain, V. K.; Nhagat, S.;
Chakraborti, A. K. Green Chem. 2013, 15, 2872.
(3) For the use of the method in the synthesis of a chiral
pharmaceutical product, see: Rossi, S.; Benaglia, M.; Porta, R.; Cotarca,
L.; Maragni, P.; Verzini, M. Eur. J. Org. Chem. 2015, 2015, 2531.
(4) Reviews: (a) Guizzetti, S.; Benaglia, M. Eur. J. Org. Chem. 2010,
2010, 5529. (b) Jones, S.; Warner, C. J. A. Org. Biomol. Chem. 2012,
10, 2189.
(21) (a) See ref 18; see also (b) Zhou, W.; Fan, M.; Yin, J.; Jiang, Y.;
Ma, D. J. Am. Chem. Soc. 2015, 137, 11942.
(5) For the most recent contributions of our group in the field see:
(a) Genoni, A.; Benaglia, M.; Massolo, E.; Rossi, S. Chem. Commun.
2013, 49, 8365. (b) Barrulas, P. C.; Genoni, A.; Benaglia, M.; Burke, A.
Eur. J. Org. Chem. 2014, 2014, 7339.
(6) Review: (a) Rossi, S.; Benaglia, M.; Genoni, A. Tetrahedron 2014,
70, 2065. For a review on Lewis base-catalyzed reactions:
(b) Denmark, S. E.; Beutner, G. L. Angew. Chem., Int. Ed. 2008, 47,
1560. (c) Beutner, G. L.; Denmark, S. E. Angew. Chem., Int. Ed. 2013,
52, 9086.
(7) As evidence that the H atom in HSiCl3 seems to be a proton
1
rather than a hydride, unless activated by Lewis bases, the H NMR
chemical shift of HSiCl3 in CDCl3 shows a singlet at 6.1 ppm, a value
too high to be assigned to a hydride.
(8) Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev. 2003,
(9) (a) Bernstein, C. S. J. Am. Chem. Soc. 1970, 92, 699. (b) Benkeser,
R. A.; Smith, W. E. J. Am. Chem. Soc. 1969, 91, 1556. (c) Benkeser, R.
A.; Smith, W. E. J. Am. Chem. Soc. 1968, 90, 5307. (d) Benkeser, R. A.;
Gaul, J. M.; Smith, W. E. J. Am. Chem. Soc. 1969, 91, 3666.
(e) Benkeser, R. A.; Foley, K. M.; Gaul, J. M.; Li, G. S.; Smith, W. E. J.
Am. Chem. Soc. 1969, 91, 4578.
(10) Karsch, H. H.; Schluter, P. A.; Bienlein, F.; Herker, M.; Witt, E.;
̈
Sladek, A.; Heckel, M. Z. Anorg. Allg. Chem. 1998, 624, 295.
(11) (a) Ghadwal, R. S.; Roesky, H. W.; Merkel, S.; Henn, J.; Stalke,
D. Angew. Chem., Int. Ed. 2009, 48, 5683. (b) Roy, S.; Stollberg, P.;
Irmer, R. H.; Stalke, D.; Andrada, D. M.; Frenking, G.; Roesky, H. W.
J. Am. Chem. Soc. 2015, 137, 150. (c) Roy, S.; Stuckl, A. C.; Demeshko,
̈
E
J. Org. Chem. XXXX, XXX, XXX−XXX