Organic Letters
Letter
Scheme 8. Proposed Reaction Mechanism
REFERENCES
■
(1) (a) Trost, B. M.; Tracy, J. S. Isr. J. Chem. 2018, 58, 18.
(b) Godoi, B.; Schumacher, R. F.; Zeni, G. Chem. Rev. 2011, 111,
2937. (c) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285.
(2) (a) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104,
3079. (b) Labonne, A.; Kribber, T.; Hintermann, L. Org. Lett. 2006, 8,
5853. (c) Grotjahn, D. B.; Lev, D. A. J. Am. Chem. Soc. 2004, 126,
12232. (d) Zhurakovskyi, O.; Dias, R. M. P.; Noble, A.; Aggarwal, V.
K. Org. Lett. 2018, 20, 3136. (e) Li, J.; Wang, C.; Xue, D.; Wei, Y.;
Xiao, J. Green Chem. 2013, 15, 2685. (f) Zeng, M.; Herzon, S. B. J.
Org. Chem. 2015, 80, 8604. (g) Li, L.; Herzon, S. B. J. Am. Chem. Soc.
2012, 134, 17376.
(3) (a) Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH:
Weinheim, Germany, 2000. (b) Tatton, M. R.; Simpson, I.; Donohoe,
T. Org. Lett. 2014, 16, 1920. (c) Brenzovich, W. E. Angew. Chem., Int.
Ed. 2012, 51, 8933. (d) Vinoth, P.; Nagarajan, S.; Maheswari, C. U.;
Sudalai, A.; Pace, V.; Sridharan, V. Org. Lett. 2016, 18, 3442.
(4) (a) Kutscheroff, M. Ber. Dtsch. Chem. Ges. 1881, 14, 1540.
(b) Budde, W. L.; Dessy, R. E. J. Am. Chem. Soc. 1963, 85, 3964.
(c) Stork, G.; Borch, R. J. Am. Chem. Soc. 1964, 86, 935.
(5) (a) Wu, X.-F.; Bezier, D.; Darcel, C. Adv. Synth. Catal. 2009,
351, 367. (b) Cabrero-Antonino, J. R.; Leyva-Perez, A.; Corma, A.
Chem. - Eur. J. 2012, 18, 11107.
(6) (a) Shimada, T.; Yamamoto, Y. J. Am. Chem. Soc. 2002, 124,
12670. (b) Xu, C.; Du, W.; Zeng, Y.; Dai, B.; Guo, H. Org. Lett. 2014,
16, 948.
(7) (a) Hiscox, W.; Jennings, P. W. Organometallics 1990, 9, 1997.
(b) Baidossi, W.; Lahav, M.; Blum, J. J. Org. Chem. 1997, 62, 669.
(8) (a) Grotjahn, D. B.; Incarvito, C. D.; Rheingold, A. L. Angew.
Chem., Int. Ed. 2001, 40, 3884. (b) Chevallier, F.; Breit, B. Angew.
Chem., Int. Ed. 2006, 45, 1599.
(9) (a) Marion, N.; Ramon, R. S.; Nolan, S. P. J. Am. Chem. Soc.
2009, 131, 448. (b) Gatto, M.; Belanzoni, P.; Belpassi, L.; Biasiolo, L.;
Del Zotto, A.; Tarantelli, F.; Zuccaccia, D. ACS Catal. 2016, 6, 7363.
(10) (a) Ackermann, L.; Kaspar, L. T. J. Org. Chem. 2007, 72, 6149.
(b) Tillack, A.; Castro, I. G.; Hartung, C. G.; Beller, M. Angew. Chem.,
Int. Ed. 2002, 41, 2541.
(11) (a) Hirabayashi, T.; Okimoto, Y.; Saito, A.; Morita, M.;
Sakaguchi, S.; Ishii, Y. Tetrahedron 2006, 62, 2231. (b) Kanemitsu,
H.; Uehara, K.; Fukuzumi, S.; Ogo, S. J. Am. Chem. Soc. 2008, 130,
17141.
(12) (a) Tachinami, T.; Nishimura, T.; Ushimaru, R.; Noyori, R.;
Naka, H. J. Am. Chem. Soc. 2013, 135, 50. (b) Lin, Z.; Zhang, Z.-M.;
Chen, Y.-S.; Lin, W. Angew. Chem., Int. Ed. 2016, 55, 13739.
(13) (a) Thuong, M. B. T.; Mann, A.; Wagner, A. Chem. Commun.
2012, 48, 434. (b) Chen, Z.-W.; Ye, D.-N.; Qian, Y.-P.; Ye, M.; Liu,
L.-X. Tetrahedron 2013, 69, 6116.
(14) (a) Jin, X.; Oishi, T.; Yamaguchi, K.; Mizuno, N. Chem. - Eur. J.
2011, 17, 1261. (b) Hintermann, L.; Labonne, A. Synthesis 2007, 38,
112.
rearrangement with the concomitant tautomerization of enolic
species C to afford the hydrated product 2.
In summary, we have described a metal-free, carbonyl-
assisted synthesis of structurally diversified di-/tricarbonyl
compounds by the regioselective hydration of o-alkynylalde-
hydes under mild conditions in good to excellent yields. The
protocol is atom economical and environment-friendly and has
been successfully extended for the one-pot synthesis of
biologically potential γ-carbolines, 5-azaindoles, and diazacar-
bazoles. The key steps involved in the reaction have been
supported by control experiments. Synthetically, this reaction
holds much promise due to its ease of operation and simplicity.
The synthesized molecules containing carbonyls along with
−Cl provide a synthetically useful handle for further
modification.
ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
1
Data and spectral copies of H, 13C NMR, and HRMS
for target compounds (PDF)
Accession Codes
crystallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(15) (a) Ghosh, N.; Nayak, S.; Sahoo, A. K. Chem. - Eur. J. 2013, 19,
9428. (b) Shen, C.-H.; Li, L.; Zhang, W.; Liu, S.; Shu, C.; Xie, Y.-E.;
Yu, Y.-F.; Ye, L.-W. J. Org. Chem. 2014, 79, 9313. (c) Hashmi, A. S. K.
Chem. Rev. 2007, 107, 3180.
(16) (a) Tsuchimoto, T.; Joya, T.; Shirakawa, E.; Kawakami, Y.
Synlett. 2000, 1777. (b) Olivi, N.; Thomas, E.; Peyrat, J.-F.; Alami,
M.; Brion, J.-D. Synlett 2004, 2175. (c) Liang, S.; Hammond, G. B.;
Xu, B. Chem. Commun. 2015, 51, 903. (d) Deng, T.; Wang, C.-Z.
Catal. Sci. Technol. 2016, 6, 7029.
AUTHOR INFORMATION
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Corresponding Author
ORCID
Author Contributions
(17) Vasudevan, A.; Verzal, M. K. Synlett 2004, 4, 631.
(18) (a) Kim, I.; Lee, C. Angew. Chem. 2013, 125, 10207. (b) Zhang,
Z.; Wu, L.; Liao, J.; Wu, W.; Jiang, H.; Li, J. J. Org. Chem. 2015, 80,
7594. (c) Ying, J.; Wang, H.; Qi, X.; Peng, J. − B.; Wu, X. − F.
Organometallics 2018, 37, 2837. (d) Ghosh, N.; Nayak, S.; Sahoo, A.
K. J. Org. Chem. 2011, 76, 500. (e) Ying, J.; Pu, L. J. Org. Chem. 2016,
81, 8135. (f) Buksnaitiene, R.; Cikotiene, I. Synlett 2011, 2011, 2529.
(19) Zhao, S.-B.; Wang, S. Chem. Soc. Rev. 2010, 39, 3142.
†S.V. and M.K. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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The Research work was supported by SERB (EMR/2017/
003218/OC) and University of Delhi. S.V., M.K., and P.K.M.
are thankful to CSIR and UGC respectively for fellowships.
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(20) Merour, J.-Y.; Buron, F.; Ple, K.; Bonnet, P.; Routier, S.
Molecules 2014, 19, 19935.
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