Organic Letters
Letter
showcased in the monodeoxygenation of three diepoxides, which
is unprecedented in the literature and would be very useful in
deciding the protection/deprotection technology of alkenes in
natural product synthesis. When compared to the prior catalytic
deoxygenation, this new catalysis system features (1) stereo-
specificity; (2) chemo- and regioselectivity; (3) broad substrate
scope (30 examples); and (4) the use of inexpensive, earth-
abundant transition-metal copper as the catalyst. These features
would make the new catalytic protocols a good choice for
deoxygenation in organic synthesis.
(9) Mu
996, 521.
10) (a) Mazet, C.; Ko
4, 4888. (b) Xu, Z.; Zhu, S.; Sun, X.; Tang, Y.; Dai, L. Chem. Commun.
007, 1960.
11) (a) Diaz-Requejo, M. M.; Mairena, M. A.; Belderrain, T. R.;
Nicasio, M. C.; Trofimenko, S.; Perez, P. J. Chem. Commun. 2001, 1804.
b) Rodriguez, P.; Caballero, A.; Diaz-Requejo, M. M.; Nicasio, M. C.;
Perez, P. J. Org. Lett. 2006, 8, 557.
(12) (a) Suarez, A.; Fu, G. C. Angew. Chem., Int. Ed. 2004, 43, 3580.
(b) Xiao, Q.; Xia, Y.; Li, H.; Zhang, Y.; Wang, J. Angew. Chem., Int. Ed.
011, 50, 1114. (c) Ye, F.; Ma, X.; Xiao, Q.; Li, H.; Zhang, Y.; Wang, J. J.
Am. Chem. Soc. 2012, 134, 5742.
13) (a) Mack, D. J.; Batory, L. A.; Njardarson, J. T. Org. Lett. 2012, 14,
78. (b) Ilardi, E. A.; Njardarson, J. T. J. Org. Chem. 2013, 78, 9533−
̈
ller, S.; Liepold, B.; Roth, G. J.; Bestmann, H. J. Synlett 1996,
1
(
4
2
̈
hler, V.; Pfaltz, A. Angew. Chem., Int. Ed. 2005,
(
(
́
2
ASSOCIATED CONTENT
Supporting Information
■
(
3
*
S
9540. (c) Mustard, T. J. L.; Mack, D. J.; Njardarson, J. T.; Cheong, P. H.
Y. J. Am. Chem. Soc. 2013, 135, 1471. (d) Guo, B.; Schwarzwalder, G.;
Njardarson, J. T. Angew. Chem., Int. Ed. 2012, 51, 5675. (e) Brichacek,
M.; Batory, L. A.; Njardarson, J. T. Angew. Chem., Int. Ed. 2010, 49, 1648.
spectra, and DFT calculations (PDF)
(14) Park, E. J.; Kim, S. H.; Chang, S. J. Am. Chem. Soc. 2008, 130,
1
7268.
AUTHOR INFORMATION
(15) For a recent review, see: Zhao, X.; Zhang, Y.; Wang, J. Chem.
■
Commun. 2012, 48, 10162.
16) (a) Lebel, H.; Marcoux, J.-F.; Molinaro, C.; Charette, A. B. Chem.
Rev. 2003, 103, 977. (b) Yang, M.; Webb, T. R.; Livant, P. J. Org. Chem.
001, 66, 4945.
(
*
2
Notes
(17) (a) Yang, M.; Webb, T. R.; Livant, P. J. Org. Chem. 2001, 66, 4945.
b) Anciaux, A. J.; Demonceau, A.; Noels, A. F.; Hubert, A. J.; Warin, R.;
(
The authors declare no competing financial interest.
Teyssie, P. J. Org. Chem. 1981, 46, 873. (c) Lovely, C. J.; Browning, R.
G.; Badarinarayana, V.; Rasika Dias, H. V. Tetrahedron Lett. 2005, 46,
2453. (d) Reisman, S. E.; Nani, R. R.; Levin, S. Synlett 2011, 2011, 2437.
(18) Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417. Also see
ref 8.
ACKNOWLEDGMENTS
This research was financially supported by the Research Grant
Council of Hong Kong (ECS 605912 and GRF 16304416).
■
(
19) For recent reviews on NHC−Cu complexes, see: (a) Lin, J. C. Y.;
Huang, R. T. W.; Lee, C. S.; Bhattacharyya, A.; Hwang, W. S.; Lin, I. J. B.
REFERENCES
■
Chem. Rev. 2009, 109, 3561. (b) Gaillard, S.; Cazin, C. S. J.; Nolan, S. P.
(
1) (a) Corey, E. J.; Su, W. G. J. Am. Chem. Soc. 1987, 109, 7534.
b) Kraus, G. A.; Thomas, P. J. J. Org. Chem. 1988, 53, 1395.
Acc. Chem. Res. 2012, 45, 778. (c) Díez-Gonzal
Aldrichimica Acta 2008, 41, 43. (d) Zhang, L.; Hou, Z. Chem. Sci. 2013,
, 3395.
20) We speculate that Cu (TFA) was reduced by a diazo compound
́
ez, S.; Nolan, S. P.
(
(
c) Johnson, W. S.; Plummer, M. S.; Reddy, S. P.; Bartlett, W. R. J. Am.
4
(
Chem. Soc. 1993, 115, 515. (d) Song, L.; Liu, Y.; Tong, R. Org. Lett. 2013,
5, 5850.
2) For an excellent review, see: (a) Wong, H. N. C.; Fok, C. C. M.;
Wong, T. Heterocycles 1987, 26, 1345.
3) For Rh-catalyzed deoxygenation of epoxides, see: (a) Martin, M.
II
2
1
(
I
to a Cu −carbene complex as a reactive catalyst. For a related reduction,
see: (a) Salomon, R. G.; Kochi, J. K. J. Am. Chem. Soc. 1973, 95, 3300.
(
b) Kirmse, W. Angew. Chem., Int. Ed. 2003, 42, 1088.
21) Lacour et al. proposed a carbocationic intermediate in the Ru-
catalyzed carbene insertions into epoxides; see: Achard, T.; Tortoreto,
C.; Poblador-Bahamonde, A. I.; Guenee, L.; Burgi, T.; Lacour, J. Angew.
Chem., Int. Ed. 2014, 53, 6140.
22) For Lewis acid catalyzed oxetane fragmentation, see: (a) van
Schaik, H.-P.; Vijn, R.-J.; Bickelhaupt, F. Angew. Chem., Int. Ed. Engl.
994, 33, 1611. For rhodium-catalyzed oxetane opening reaction, see:
b) Rix, D.; Ballesteros-Garrido, R.; Zeghida, W.; Besnard, C.; Lacour, J.
Angew. Chem., Int. Ed. 2011, 50, 7308.
23) For other DFT mechanistic studies on deoxygenation of epoxides,
see: (a) Bi, S.; Wang, J.; Liu, L.; Li, P.; Lin, Z. Organometallics 2012, 31,
139. (b) Su, M.-D.; Chu, S.-Y. Chem. - Eur. J. 2000, 6, 3777.
24) For cycloreversion of oxetanes, see: (a) Adames, G.; Bibby, C.;
(
(
G.; Ganem, B. Tetrahedron Lett. 1984, 25, 251. For recent Re-catalyzed
deoxygenation of epoxides, see: (b) Ziegler, J. E.; Zdilla, M. J.; Evans, A.
J.; Abu-Omar, M. M. Inorg. Chem. 2009, 48, 9998 and references cited
therein.
́
́
̈
(
(
4) Nakagiri, T.; Murai, M.; Takai, K. Org. Lett. 2015, 17, 3346.
(
5) (a) Mitsudome, T.; Noujima, A.; Mikami, Y.; Mizugaki, T.;
1
Jitsukawa, K.; Kaneda, K. Angew. Chem., Int. Ed. 2010, 49, 5545.
(
(
b) Noujima, A.; Mitsudome, T.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K.
Angew. Chem., Int. Ed. 2011, 50, 2986. (c) Ni, J.; He, L.; Liu, Y.-M.; Cao,
Y.; He, H.-Y.; Fan, K.-N. Chem. Commun. 2011, 47, 812. (d) Mitsudome,
T.; Mikami, Y.; Matoba, M.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K.
Angew. Chem., Int. Ed. 2012, 51, 136.
(
6
(
(
6) (a) Chirik, P.; Morris, R. Acc. Chem. Res. 2015, 48, 2495. For
selected examples, see: (b) Jagadeesh, R. V.; Surkus, A.-E.; Junge, H.;
Pohl, M.-M.; Radnik, J.; Rabeah, J.; Huan, H.; Schunemann, V.;
Bruckner, A.; Beller, M. Science 2013, 342, 1073. (c) Friedfeld, M. R.;
Shevlin, M.; Hoyt, J. M.; Krska, S. W.; Tudge, M. T.; Chirik, P. J. Science
Grigg, R. J. Chem. Soc., Chem. Commun. 1972, 491. (b) Jones, G., II;
Schwartz, S. B.; Marton, M. T. J. Chem. Soc., Chem. Commun. 1973, 374.
c) Jones, G., II; Acquadro, M. A.; Carmody, M. A. J. Chem. Soc., Chem.
Commun. 1975, 0, 206. (d) Perez-Ruiz, R.; Izquierdo, M. A.; Miranda,
̈
(
̈
M. A. J. Org. Chem. 2003, 68, 10103. (e) Perez-Ruiz, R.; Gil, S.; Miranda,
2
2
013, 342, 1076. (d) Zuo, W.; Lough, A. J.; Li, Y. F.; Morris, R. H. Science
013, 342, 1080.
M. A. J. Org. Chem. 2005, 70, 1376. (f) Per
Domingo, L. R.; Jimenez, M. C.; Miranda, M. A. Org. Lett. 2012, 14,
700.
́ ́
ez-Ruiz, R.; Saez, J. A.;
(
7) Tamao, K.; Nakajo, E.; Ito, Y. J. Org. Chem. 1988, 53, 414.
5
(
8) Allen, S. E.; Walvoord, R. R.; Padilla-Salinas, R.; Kozlowski, M. C.
Chem. Rev. 2013, 113, 6234. (b) Evano, G.; Theunissen, C.; Pradal, A.
Nat. Prod. Rep. 2013, 30, 1467. (c) Zhang, D.-Y.; Hu, X.-P. Tetrahedron
Lett. 2015, 56, 283. (d) Sambiagio, C.; Marsden, S. P.; Blacker, A. J.;
McGowan, P. C. Chem. Soc. Rev. 2014, 43, 3525. (e) Deutsch, C.;
Krause, N.; Lipshutz, B. H. Chem. Rev. 2008, 108, 2916.
D
Org. Lett. XXXX, XXX, XXX−XXX