Organic Letters
Letter
(6) For selected examples of gold-catalyzed oxidation, see: (a) Wu, G.;
Zheng, R.; Nelson, J.; Zhang, L. Adv. Synth. Catal. 2014, 356, 1229. (b) Ji,
K.; D’Souza, B.; Nelson, J.; Zhang, L. J. Organomet. Chem. 2014, 770, 142.
(c) Liu, Y. In Modern Gold Catalyzed Synthesis; Hashmi, A. S. K., Toste, F.
D., Ed.; Wiley-VCH: Weinheim, 2012; p 263. (d) Wang, Y.; Ji, K.; Lan,
S.; Zhang, L. Angew. Chem., Int. Ed. 2012, 51, 1915. (e) Li, Z.; Brouwer,
C.; He, C. Chem. Rev. 2008, 108, 3239.
(7) (a) Obradors, C.; Echavarren, A. M. Acc. Chem. Res. 2014, 47, 902.
(b) Motika, S. E.; Wang, Q.; Ye, X.; Shi, X. Org. Lett. 2015, 17, 290.
(8) (a) Hashmi, A. S. K.; Sinha, P. Adv. Synth. Catal. 2004, 346, 432.
(b) Gonzalez, M. J.; Gonzalez, J.; Vicente, R. Eur. J. Org. Chem. 2012,
6140.
oximes. Terminal alkynes underwent a 6-exo-dig cyclization
reaction giving rise to the formation of pyrazine N-oxides. This
synthetic strategy represents a reasonable methodology for the
construction of hitherto unknown skeletons. However, in the
case of substituted alkynes, the reaction proceeded in a
completely different way forming an intermediate with a seven-
membered ring, which transfers the oxime functionality intra-
molecularly from one carbon to another. This type of
rearrangement has not been previously observed and represents
a new rearrangement, the oxime−oxime rearrangement.
(9) (a) Gomez-Suarez, A.; Gasperini, D.; Vummaleti, S. V. C.; Poater,
A.; Cavallo, L.; Nolan, S. P. ACS. Catal. 2014, 4, 2701. (b) Sherry, B. D.;
Toste, F. D. J. Am. Chem. Soc. 2004, 126, 15978. (c) Krafft, M. E.; Hallal,
K. M.; Vidhani, D. V.; Cran, J. W. Org. Biomol. Chem. 2011, 9, 7535.
(d) Shi, M.; Wu, L.; Lu, J. J. Org. Chem. 2008, 73, 8344. (e) Lu, B.; Shi, M.
Chem.Eur. J. 2010, 16, 10975. (f) Lopez, S. S.; Engel, D. A.; Dudley, G.
B. Synlett 2007, 6, 949. (g) Pennell, M. N.; Turner, P. G.; Sheppard, T. D.
Chem.Eur. J. 2012, 18, 4748. (h) Ramon, R. S.; Gaillard, S.; Slawin, A.
M. Z.; Porta, A.; D’Alfonso, A.; Zanoni, G.; Nolan, S. P. Organometallics
2010, 29, 3665. (i) Felix, R. J.; Weber, D.; Gutierrez, O.; Tantillo, D. J.;
ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental conditions, spectroscopic data (1D and 2D NMR
spectra) of the products, Cartesian coordinates for the optimized
structures. This material is available free of charge via the Internet
́
Gagne, M. R. Nat. Chem. 2012, 5, 405. (j) Bae, H. J.; Jeong, W.; Lee, J. H.;
AUTHOR INFORMATION
Rhee, Y. H. Chem.Eur. J. 2011, 17, 1433−1436. (k) Jimenez-Nunez,
E.; Claverie, C. K.; Bour, C.; Cardenas, D. J.; Echavarren, A. M. Angew.
Chem., Int. Ed. 2008, 47, 7892. (l) Tang, J.; Bhunia, S.; Sohel, S. A.; Lin,
M.; Liao, H.; Datta, S.; Das, A.; Liu, R. J. Am. Chem. Soc. 2007, 129,
15677.
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Corresponding Author
Notes
(10) Menges, N.; Sari, O.; Abdullayev, Y.; Erdem, S. S.; Balci, M. J. Org.
Chem. 2013, 78, 5184.
The authors declare no competing financial interest.
(11) Cetinkaya, Y.; Balci, M. Tetrahedron Lett. 2014, 55, 6698.
(12) Beckmann, E. Ber. Dtsch. Chem. Ges. 1886, 19, 988.
(13) For a review on metal-catalyzed Beckmann rearrangement, see:
Pascale Crochet, P.; Cadierno, V. Chem. Commun. 2015, 51, 2495.
(14) Park, S.; Choi, Y.; Han, H.; Yang, S. H.; Chang, S. Chem. Commun.
2003, 1936.
(15) Owston, N. A.; Parker, A. J.; Williams, J. M. J. Org. Lett. 2007, 9, 73.
(16) Gnanamgari, D.; Crabtree, R. H. Organometallics 2009, 28, 922.
(17) Ali, M. A.; Punniyamurthy, T. Adv. Synth. Catal. 2010, 352, 288.
(18) (a) Raja, N.; Therrien, B. J. Organomet. Chem. 2014, 765, 1.
(b) Tambara, K.; Pantos, G. D. Org. Biomol. Chem. 2013, 11, 2466. (c) Li,
Y.-T.; Liao, B.-S.; Chen, H.-P.; Liu, S.-T. Synthesis 2011, 2639. (d) Jiang,
N.; Ragauskas, A. J. Tetrahedron Lett. 2010, 51, 4479. (e) Kim, H. S.; Kim,
S. H.; Kim, J. M. Tetrahedron Lett. 2009, 50, 1717.
ACKNOWLEDGMENTS
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Financial support from the Scientific and Technological Research
Council of Turkey (TUBITAK, Grant No. TBAG-112 T360),
the Turkish Academy of Sciences (TUBA), and Middle East
Technical University (METU) is gratefully acknowledged. We
also thank Research Assistant Ozlem Sari (METU) for her help
with calculations.
REFERENCES
■
(1) (a) Trost, B. M. Science 1991, 254, 1471. (b) Trost, B. M. Angew.
Chem., Int. Ed. 1995, 34, 259. (c) Trost, B. M. Acc. Chem. Res. 2002, 35,
695.
(2) (a) Alcaide, B.; Almendros, P.; Quiros, M. T.; Fernandez, I. Beilstein
J. Org. Chem. 2013, 9, 818. (b) Rudolph, M. In Modern Gold Catalyzed
Synthesis; Hashmi, A. S. K., Toste, F. D., Ed.; Wiley-VCH: Weinheim,
2012; p 331. (c) Barluenga, J.; Siguerio, R.; Vicente, R.; Ballesteros, A.;
Tomas, M.; Rodriguez, M. A. Angew. Chem., Int. Ed. 2012, 51, 10377.
(d) Fortman, G. C.; Nolan, S. P. Chem. Soc. Rev. 2011, 132, 5151.
(19) (a) Ramon
Nolan, S. P. J. Org. Chem. 2010, 75, 1197. (b) Gaillard, S.; Bosson, J.;
Ramon
́ ́
, R. S.; Bosson, J.; Díez-Gonzalez, S.; Marion, N.;
́
, R. S.; Nun, P.; Slawin, A. M. Z.; Nolan, Z. P. Chem.Eur. J.
2010, 16, 13729.
̈
(20) (a) Chinchilla, R.; Najera, C. Chem. Rev. 2007, 107, 874.
(b) Douchet, H.; Hierso, J.-C. Angew. Chem., Int. Ed. 2007, 46, 834.
(c) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 16,
4467. (d) Caporale, A.; Tartaggia, S.; Castellin, A.; de Lucchi, O. Beilstein
J. Org. Chem. 2014, 10, 384.
(e) Alcarazo, M.; Stork, T.; Anoop, A.; Thiel, W.; Furstner, A. Angew.
Chem., Int. Ed. 2010, 49, 2542. (f) Hashmi, A. S. K. Chem. Rev. 2007, 107,
3180.
̈
́
(21) (a) Kuuloja, N.; Tois, J.; Franzen, R. Tetrahedron Asymmetry 2011,
(3) (a) Siah, H.-S. M.; Kaur, M.; Iqbal, N.; Fiksdahl, A. Eur. J. Org. Chem.
2014, 1727. (b) Shapiro, N. D.; Shi, Y.; Toste, F. D. J. Am. Chem. Soc.
2009, 131, 11654. (c) Kim, N.; Kim, Y.; Park, W.; Sung, D.; Gupta, A. K.;
Oh, C. H. Org. Lett. 2005, 7, 5289. (d) Zhang, G.; Zhang, L. J. Am. Chem.
Soc. 2008, 130, 12598.
(4) For selected examples of gold-catalyzed Friedel−Crafts reaction,
see: (a) Hashmi, A. S. K.; Schwarz, L.; Choi, J. H.; Frost, T. M. Angew.
Chem., Int. Ed. 2000, 39, 2285. (b) Hashmi, A. S. K.; Blanco, M. C. Eur. J.
Org. Chem. 2006, 4340. (c) Nguyen, R. V.; Yao, X. Q.; Li, C. J. Org. Lett.
2006, 8, 2397.
(5) For selected examples of gold-catalyzed C−H activation, see:
(a)Hashmi, A. S. K. Acc. Chem. Res. 2014, 47, 864. (b) Wencel-Delord, J.;
Glorius, F. Nat. Chem. 2013, 5, 369. (c) Yamaguchi, J.; Yamaguchi, A. D.;
Itami, K. Angew. Chem., Int. Ed. 2012, 51, 8960. (d) Boorman, T. C.;
Larrosa, I. Chem. Soc. Rev. 2011, 40, 1910. (e) Godula, K.; Sames, D.
Science 2006, 312, 67.
22, 468. (b) Tsotinis, A.; Afroudakis, P. A.; Davidson, K.; Prashar, A.;
Sugden, D. J. Med. Chem. 2007, 50, 6436. (c) Acid, L.; Reactions, C.;
Rearrangement, N. O. J. Org. Chem. 1990, 46, 4255. (d) Agnusdei, M.;
Bandini, M.; Melloni, A.; Umani-Ronchi, A. J. Org. Chem. 2003, 68, 7126.
(22) Karabatsos, G. J.; Taller, R. A. Tetrahedron 1967, 24, 3347.
(23) Butler, M.; Cabrera, G. M. J. Mol. Struct. 2013, 1042, 37 and
references therein.
(24) Thomas, R. J.; Campbell, K. N.; Hennion, G. F. J. Am. Chem. Soc.
1938, 60, 718.
(25) Bez, G.; Gogoi, D. Tetrahedron Lett. 2006, 47, 5155.
(26) Corey, E. J.; Seebach, D.; Freedman, R. J. Am. Chem. Soc. 1967, 89,
434.
(27) Basceken, S.; Balci, M. J. Org. Chem. 2015, 80, 3806.
D
Org. Lett. XXXX, XXX, XXX−XXX