Organic Letters
Letter
T. Chem. - Eur. J. 2016, 22, 12278. (f) Li, Z.; Yazaki, R.; Ohshima, T.
Org. Lett. 2016, 18, 3350.
Discovery, Informatics, and Structural Life Science from
AMED, and Naito Foundation. M.N. and Y.S. thank JSPS for
Research Fellowships for Young Scientists. We thank the
research group of Prof. Go Hirai at Kyushu University for the
use of a polarimeter and Prof. Stephen C. Bergmeier at Ohio
University for helpful discussions.
(14) For selected examples of cleavage of activated carbamate moiety
in the presence of amide bonds, see: (a) Hsi, R. S. P.; Brown, L. W.;
Kagan, F.; Hanze, A. R.; Stafford, J. E.; Forist, A. A. J. Org. Chem. 1972,
37, 3427. (b) Hegarty, A. F.; Frost, L. N.; Coy, J. H. J. Org. Chem.
1974, 39, 1089. (c) Evans, D. A.; Britton, T. C.; Ellman, J. A.
Tetrahedron Lett. 1987, 28, 6141. For the cleavage of unactivated
carbamate in the presence of amide but in moderate yields (38−40%),
REFERENCES
■
see: (d) de la Fuente, A.; Martin, R.; Mena-Barragan
X.; Fernandez, J. M. G.; Mellet, C. O.; Riera, A. Org. Lett. 2013, 15,
3638.
́
, T.; Verdaguer,
(1) For reviews, see: (a) Ghosh, A. K.; Brindisi, M. J. Med. Chem.
2015, 58, 2895 and references cited therein. (b) Wang, N.; Budde, W.
L. Anal. Chem. 2001, 73, 997.
́
(15) For the formal cleavage of urea moiety in the presence of amide
bonds under related conditions, see: (a) Shealy, Y. F.; Clayton, J. D. J.
Org. Chem. 1964, 29, 2141. For the cleavage of urea moiety in the
presence of hydrazide but in low yield (17%), see: (b) Sunder, S.; Peet,
N. P. J. Org. Chem. 1977, 42, 2551. For selected examples of cleavage
of activated urea moiety in the presence of amide bonds, see:
(c) Ulrich, H.; Tucker, B.; Richter, R. J. Org. Chem. 1978, 43, 1544.
(d) Hirota, K.; Abe, Y.; Asao, T.; Senda, S.; Kitade, Y.; Maki, Y. J.
Heterocycl. Chem. 1988, 25, 985. (e) Jursic, B. S.; Neumann, D. M.;
Moore, Z.; Stevens, E. D. J. Org. Chem. 2002, 67, 2372. (f) Beria, I.;
Nesi, M. Tetrahedron Lett. 2002, 43, 7323. (g) Kamata, J.; Okada, T.;
Kotake, Y.; Niijima, J.; Nakamura, K.; Uenaka, T.; Yamaguchi, A.;
Tsukahara, K.; Nagasu, T.; Koyanagi, N.; Kitoh, K.; Yoshimatsu, K.;
Yoshino, H.; Sugumi, H. Chem. Pharm. Bull. 2004, 52, 1071. (h) Hartz,
R. A.; Nanda, K. K.; Ingalls, C. L.; Ahuja, V. T.; Molski, T. F.; Zhang,
G.; Wong, H.; Peng, Y.; Kelley, M.; Lodge, N. J.; Zaczek, R.; Gilligan,
P. J.; Trainor, G. L. J. Med. Chem. 2004, 47, 4741. (i) Bhandari, M. R.;
Sivappa, R.; Lovely, C. J. Org. Lett. 2009, 11, 1535.
(16) Although the reason for the observed chemoselectivity has not
yet been clarified, we assume that carbamates and ureas are more
prone to react with nitrogen nucleophiles than amides in the absence
of Brønsted acids. It is also noted that formation of an isocyanate
intermediate as the origin of the chemoselectivity is less likely because
a competitive reaction between tertiary carbamate and tertiary amide
preferentially cleaved carbamate under the present reaction con-
ditions.11
(2) Wuts, P. G. M. Greene’s Protective Groups in Organic Synthesis, 5th
ed.; John Wiley & Sons: Hoboken, 2014; pp 907−990 and 1116−
1119.
(3) For reviews, see: (a) Gnas, Y.; Glorius, F. Synthesis 2006, 2006,
1899 and references therein. (b) Lait, S. M.; Rankic, D. A.; Keay, B. A.
Chem. Rev. 2007, 107, 767.
(4) For selected reviews, see: (a) Snieckus, V. Chem. Rev. 1990, 90,
879. (b) Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417.
(c) Du Bois, J. Org. Process Res. Dev. 2011, 15, 758. (d) Volz, N.;
Clayden, J. Angew. Chem., Int. Ed. 2011, 50, 12148. (e) Yamaguchi, J.;
Yamaguchi, A. D.; Itami, K. Angew. Chem., Int. Ed. 2012, 51, 8960.
(f) Ramirez, T. A.; Zhao, B.; Shi, Y. Chem. Soc. Rev. 2012, 41, 931.
(5) Mabey, W.; Mill, T. J. Phys. Chem. Ref. Data 1978, 7, 383.
(6) (a) Karplus, P. A.; Pearson, M. A.; Hausinger, R. P. Acc. Chem.
Res. 1997, 30, 330 and references cited therein. (b) Salvestrini, S.;
Cerbo, P. D.; Capasso, S. J. Chem. Soc. Perkin Trans. 2 2002, 1889.
(7) For reviews on hydrogenation of carbamates and ureas, see:
(a) Gunanathan, C.; Milstein, D. Chem. Rev. 2014, 114, 12024.
(b) Wang, W.-H.; Himeda, Y.; Muckerman, J. T.; Manbeck, G. F.;
Fujita, E. Chem. Rev. 2015, 115, 12936. For selected seminal
contributions, see: (c) Balaraman, E.; Gunanathan, C.; Zhang, J.;
Shimon, L J. W.; Milstein, D. Nat. Chem. 2011, 3, 609. (d) Balaraman,
E.; Ben-David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2011, 50, 11702.
(8) For the cleavage of carbamates using nitrogen nucleophiles as
cleaving reagents, see: (a) Shono, T.; Matsumura, Y.; Uchida, K.;
Tsubata, K.; Makino, A. J. Org. Chem. 1984, 49, 300. (b) Katz, S. J.;
Bergmeier, S. C. Tetrahedron Lett. 2002, 43, 557. (c) Suar
́
ez-Castillo,
chez-
O. R.; Montiel-Ortega, L. A.; Melendez-Rodríguez, M.; San
́
́
Zavala, M. Tetrahedron Lett. 2007, 48, 17. For selected contributions
regarding the cleavage of unactivated carbamates, see: (d) Coe, D. M.;
Perciaccante, R.; Procopiou, P. A. Org. Biomol. Chem. 2003, 1, 1106.
́ ́ ́
(e) Jacquemard, U.; Beneteau, V.; Lefoix, M.; Routier, S.; Merour, J.-
Y.; Coudert, G. Tetrahedron 2004, 60, 10039. (f) Morin, J.; Zhao, Y.;
Snieckus, V. Org. Lett. 2013, 15, 4102. For other cleavage methods,
see ref 2.
(9) For selected recent examples on the cleavage of unactivated ureas,
see: (a) Clayden, J.; Hennecke, U. Org. Lett. 2008, 10, 3567.
(b) Hutchby, M.; Houlden, C. E.; Ford, J. G.; Tyler, S. N. G.; Gagne,
́
M. R.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. Angew. Chem., Int. Ed.
́
2009, 48, 8721. (c) Fuentes de Arriba, A. L.; Seisdedos, D. G.; Simon
́
,
L.; Alcazar, V.; Raposo, C.; Moran, J. R. J. Org. Chem. 2010, 75, 8303.
For related cleavage of ureas in patent, see: (d) McDougall, P. J.;
Saenz, J.; Lao, D. US2014/73814 A1, 2014.
́
́
(10) (a) Shimizu, Y.; Morimoto, H.; Zhang, M.; Ohshima, T. Angew.
Chem., Int. Ed. 2012, 51, 8564. (b) Shimizu, Y.; Noshita, M.; Mukai, Y.;
Morimoto, H.; Ohshima, T. Chem. Commun. 2014, 50, 12623.
(12) (a) Espino, C. G.; Du Bois, J. Angew. Chem., Int. Ed. 2001, 40,
598. (b) Cui, Y.; He, C. Angew. Chem., Int. Ed. 2004, 43, 4210.
(13) For reviews on chemoselectivity, see: (a) Afagh, N. A.; Yudin, A.
K. Angew. Chem., Int. Ed. 2010, 49, 262. (b) Mahatthananchai, J.;
Dumas, A. M.; Bode, J. W. Angew. Chem., Int. Ed. 2012, 51, 10954. For
our recent contributions regarding chemoselectivity, see: (c) Uesugi,
S.; Li, Z.; Yazaki, R.; Ohshima, T. Angew. Chem., Int. Ed. 2014, 53,
1611. (d) Tokumasu, K.; Yazaki, R.; Ohshima, T. J. Am. Chem. Soc.
2016, 138, 2664. (e) Horikawa, R.; Fujimoto, C.; Yazaki, R.; Ohshima,
D
Org. Lett. XXXX, XXX, XXX−XXX