Journal of the American Chemical Society
expected less-favorable
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are
consistent
with
the
1
2
3
4
5
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7
8
iminium/enamine formation with the smaller cyclic amines. A
similar rationale accounts for the successful coupling of
piperidine and cyclopropylmethanol (37).
(9) For reviews on non-traditional strategies for amide synthesis, see:
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Overall, these results highlight the utility of new
CuI/nitroxyl catalyst systems for aerobic oxidative coupling of
alcohols and amines to amides. The unusually mild reaction
conditions (room temperature) and catalytic efficiency (30 min
– 3 h reaction times) is matched by excellent functional group
compatibility and broad substrate scope. These favorable
features combine with the commercial availability of the
catalyst components to offer a highly appealing strategy for
amide bond formation.
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ASSOCIATED CONTENT
Supporting Information. Experimental procedures and
compound characterization data. This material is available
AUTHOR INFORMATION
Corresponding Author
(12) For a heterogeneous Ag-catalyzed method, see: Shimizu, K.-i.;
Ohshima, K.; Satsuma, A. Chem. Eur. J. 2009, 15, 9977−9980.
(13) (a) Soulé, J.-F.; Miyamura, H.; Kobayashi, S. J. Am. Chem. Soc.
2011, 133, 18550−18553. (b) Soulé, J.-F.; Miyamura, H.; Kobayashi,
S. Asian J. Org. Chem. 2012, 1, 319−321. (c) Soulé, J.-F.; Miyamura,
H.; Kobayashi, S. Chem. Asian J. 2013, 8, 2614−2626.
*stahl@chem.wisc.edu
Notes
The authors declare no competing financial interests.
(14) For additional Au-catalyzed examples, see: (a) Wang, Y.; Zhu,
D.; Tang, L.; Wang, S.; Wang, Z. Angew. Chem. Int. Ed. 2011, 50,
8917−8921. (b) Zhang, L.; Wang, W.; Wang, A.; Cui, Y.; Yang, X.;
Huang, Y.; Liu, X.; Liu, W.; Son, J.-Y.; Oji, H.; Zhang, T. Green
Chem. 2013, 15, 2680−2684. (c) Wang, W.; Cong, Y.; Zhang, L.;
Huang, Y.; Wang, X.; Zhang, T. Tetrahedron Lett. 2014, 55,
124−127.
ACKNOWLEDGMENT
This work was supported by the NIH (F32-GM109569 to
S.L.Z and R01-GM100143). Spectroscopic instrumentation
was partially supported by the NIH (1S10 OD020022-1)
and the NSF (CHE-1048642)
(15) For additional precedents, see the following. Formation of 1°
amides: (a) Yamaguchi, K.; Kobayashi, H.; Oishi, T.; Mizuno, N.
Angew. Chem. Int. Ed. 2012, 51, 544−547. (b) Yamaguchi, K.;
Kobayashi, H.; Wang, Y.; Oishi, T.; Ogasawara, Y.; Mizuno, N.
Catal. Sci. Technol. 2013, 3, 318−327. Formation of benzamides: (c)
Sindhuja, E.; Ramesh, R.; Balaji, S.; Liu, Y. Organometallics 2014,
33, 4269−4278. (d) Bantreil, X.; Fleith, C.; Martinez, J.; Lamaty, F.
ChemCatChem 2012, 4, 1922−1925. (e) Liu, X.; Jensen, K. F. Green
Chem. 2013, 15, 1538−1541. (f) Wu, X.-F.; Sharif, M.; Pews-
Davtyan, A.; Langer, P.; Ayub, K.; Beller, M. Eur. J. Org. Chem.
2013, 2783−2787. (g) Gaspa, S.; Porcheddu, A.; De Luca, L. Org.
Biomol. Chem. 2013, 11, 3803−3807. (h) Arefi, M.; Saberi, D.;
Karimi, M.; Heydari, A. ACS Comb. Sci. 2015, 17, 341−347. (i)
Bantreil, X.; Navals, P.; Martinez, J.; Lamaty, F. Eur. J. Org. Chem.
2015, 417−422.
(16) Caution: Mixtures of organic solvents and O2 represent a
flammability/safety hazard. Large scale reactions should not be
performed without thorough safety analysis. For relevant discussion,
see: Osterberg, P. M.; Niemeier, J. K.; Welch, C. J.; Hawkins, J. M.;
Martinelli, J. R.; Johnson, T. E.; Root, T. W.; Stahl, S. S. Org.
Process Res. Dev. 2015, 19, 1537−1543.
(17) For use of sieves in related reactions, see:: Xu, B.; Lumb, J.-P.;
Arndtsen, B. A. Angew. Chem. Int. Ed. 2015, 54, 4208−4211.
(18) The yield was only marginally reduced with unactivated rather
than flame-dried sieves, while 4Å and 5Å sieves led to moderately
lower yields (see Supporting Information, Section III). For a previous
study in which sieves play roles other than as a desiccant, see:
Steinhoff, B. A.; King, A. E.; Stahl, S. S. J. Org. Chem. 2006, 71,
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