Organic Letters
Letter
In summary, we have developed a one-pot spirocyclization
from sulfonamides to the synthesis of azaspiro derivatives. This
chemistry tolerates a variety of alkanones as well as numerous
substituentsatthealkenylmoiety. Thus, multipleringsizesforthe
spiro derivatives are accessible. Furthermore, this strategy enables
the efficient construction of azaspirocyclic scaffolds which can be
useful building blocks for alkaloid indoles. DFT calculations gave
insights into the underlying mechanism and corroborated the
results obtained. Further studies expanding the scope and
applications of this one-pot process are ongoing inour laboratory.
Rev. 2010, 110, 5064. (b) Wang, X.-N.; Yeom, H.-S.; Fang, L.-C.; He, S.;
Ma, Z.-X.; Kedrowski, B. L.; Hsung, R. P. Acc. Chem. Res. 2014, 47, 560.
(c) Evano, G.; Blanchard, N.; Compain, G.; Coste, A.; Demmer, C. S.;
Gati, W.; Guissart, C.; Heimburger, J.; Henry, N.; Jouvin, K.;
Karthikeyan, G.; Laouiti, A.; Lecomte, M.; Martin-Mingot, A.;
Metayer, B.; Michelet, B.; Nitelet, A.; Theunissen, C.; Thibaudeau, S.;
́
Wang, J.; Zarca, M.; Zhang, C. Chem. Lett. 2016, 45, 574. (d) Evano, G.;
Coste, A.; Jouvin, K. Angew. Chem., Int. Ed. 2010, 49, 2840.
(
e) Willumstad, T. P.; Boudreau, P. D.; Danheiser, R. L. J. Org. Chem.
2015, 80, 11794. (f) Gawade, S. A.; Huple, D. B.; Liu, R. S. J. Am. Chem.
Soc. 2014, 136, 2978. (g) Theunissen, C.; Metayer, B.; Henry, N.;
́
Compain, G.; Marrot, J.; Martin-Mingot, A.; Thibaudeau, S.; Evano, G. J.
Am. Chem. Soc. 2014, 136, 12528. (h) Romain, E.; Fopp, C.; Chemla, F.;
Ferreira, F.; Jackowski, O.; Oestreich, M.; Perez-Luna, A. Angew. Chem.,
Int. Ed. 2014, 53, 11333. (i) Liu, R.; Winston-McPherson, G. N.; Yang, Z.
Y.; Zhou, X.; Song, W.; Guzei, I. A.; Tang, W. J. Am. Chem. Soc. 2013, 135,
8201. (j) Frischmuth, A.; Knochel, P. Angew. Chem., Int. Ed. 2013, 52,
ASSOCIATED CONTENT
Supporting Information
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0084. (k) Minko, Y.; Pasco, M.; Lercher, L.; Botoshansky, M.; Marek, I.
H and C NMR spectra (PDF)
Nature 2012, 490, 522. (l) Valenta, P.; Carroll, P. J.; Walsh, P. J. J. Am.
Chem. Soc. 2010, 132, 14179.
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7) Selected examples since 2010 and references therein. For
publications using Au, see: (a) Li, C. W.; Pati, K.; Lin, G. Y.; Sohel, S.
M.; Hung, H. H.; Liu, R. S. Angew. Chem., Int. Ed. 2010, 49, 9891.
AUTHOR INFORMATION
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(b) Ghosh, N.; Nayak, S.; Sahoo, A. K. Chem. - Eur. J. 2013, 19, 9428.
(c) Wang, K. B.; Ran, R. Q.; Xiu, S. D.; Li, C. Y. Org. Lett. 2013, 15, 2374.
(d) Blanco Jaimes, M. C.; Weingand, V.; Rominger, F.; Hashmi, A. S. K.
ORCID
Chem. - Eur. J. 2013, 19, 12504. (e) Adcock, H. V.; Langer, T.; Davies, P.
W. Chem. -Eur. J. 2014, 20, 7262. (f)Wang, T.;Shi, S.;Hansmann, M. M.;
Rettenmeier, E.; Rudolph, M.; Hashmi, A. S. K. Angew. Chem., Int. Ed.
Notes
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014, 53, 3715. (g) Liu, J.; Chen, M.; Zhang, L.; Liu, Y. Chem. - Eur. J.
2015, 21, 1009. (h) Tokimizu, Y.; Wieteck, M.; Rudolph, M.; Oishi, S.;
Fujii, N.; Hashmi, A. S. K.; Ohno, H. Org. Lett. 2015, 17, 604. ForPd, see:
The authors declare no competing financial interest.
(i) Greenaway, R. L.; Campbell, C. D.; Holton, O. T.; Russell, C. A.;
Anderson, E. A. Chem. - Eur. J. 2011, 17, 14366. (j) Walker, P. R.;
Campbell, C. D.; Suleman, A.; Carr, G.; Anderson, E. A. Angew. Chem.,
Int. Ed. 2013, 52, 9139. Liu, G.; Kong, W.; Che, J.; Zhu, G. Adv. Synth.
Catal. 2014, 356, 3314. For Ru, see: (l) Wakamatsu, H.; Sakagami, M.;
Hanata, M.; Takeshita, M.; Mori, M. Macromol. Symp. 2010, 293, 5. For
Cu, see:(m)Hashmi, A. S. K.;Schuster, A. M.;Zimmer, M.;Rominger, F.
Chem. - Eur. J. 2011, 17, 5511. (n) Gati, W.; Couty, F.; Boubaker, T.;
Rammah, M. M.; Rammah, M. B.; Evano, G. Org. Lett. 2013, 15, 3122.
For Rh, see: (o) Nishimura, T.; Takiguchi, Y.; Maeda, Y. Y.; Hayashi, T.
Adv. Synth. Catal. 2013, 355, 1374. (p) Seeref 3i. For Ag, see: (q) Garcia,
P.; Harrak, Y.; Diab, L.; Cordier, P.; Ollivier, C.; Gandon, V.; Malacria,
M.; Fensterbank, L.; Aubert, C. Org. Lett. 2011, 13, 2952. (r) Sueda, T.;
Kawada, A.; Urashi, Y.; Teno, N. Org. Lett. 2013, 15, 1560.
ACKNOWLEDGMENTS
Support for this work was provided by CNRS and Universite
Strasbourg. F.B. thanks M.R.T. for a research fellowship. We
thank a reviewer for a valuable suggestion.
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REFERENCES
■
(
1) The Practice of Medicinal Chemistry; Wermuth, C. G., Ed.; Elsevier
Academic Press: San Diego, 2003.
(
2) Hung, A. W.; Ramek, A.; Wang, Y.; Kaya, T.; Wilson, J. A.; Clemons,
P. A.; Young, D. W. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 6799.
3) Selected examples since 2010: (a) Giampa, G. M.; Fang, J.; Brewer,
M. Org. Lett. 2016, 18, 3952. (b) Nibbs, A. E.; Montgomery, T. D.; Zhu,
Y.; Rawal, V. H. J. Org. Chem. 2015, 80, 4928. (c) McMurray, L.; Beck, E.
M.; Gaunt, M. J. Angew. Chem. 2012, 124, 9422; Angew. Chem., Int. Ed.
(
(8) Heinrich, C. F.; Fabre, I.; Miesch, L. Angew. Chem., Int. Ed. 2016, 55,
5
170.
(
(
(
9) Yao, B.; Liang, Z.; Niu, T.; Zhang, Y. J. J. Org. Chem. 2009, 74, 4630.
10) Hirano, S.; Tanaka, R.; Urabe, H.; Sato, F. Org. Lett. 2004, 6, 727.
11) CCDC 1555872 (2h) contains the supplementary crystallo-
2
012, 51, 9288. (d) Kawano, M.; Kiuchi, T.; Negishi, S.; Tanaka, H.;
Hoshikawa, T.; Matsuo, J.; Ishibashi, H. Angew. Chem. 2013, 125, 940;
Angew. Chem., Int. Ed. 2013, 52, 906. (e) Cho, H.-K. T.; Tam, N. T.; Cho,
C.-G. Bull. Korean Chem. Soc. 2010, 31, 3382. (f) De Simone, F.; Gertsch,
J.; Waser, J. Angew. Chem., Int. Ed. 2010, 49, 5767. (g) Guer
Sabot, C.; Beaulieu, M.-A.; Giroux, M.-A.; Canesi, S. Tetrahedron 2010,
6, 5893. (h) Jones, S. B.; Simmons, B.; Mastracchio, A.; MacMillan, D.
W. C. Nature 2011, 475, 183. (i) Jiao, L.; Herdtweck, E.; Bach, T. J. Am.
Chem.Soc. 2012,134,14563.(j)Lajiness, J.P.;Jiang, W.;Boger,D. L.Org.
Lett. 2012, 14, 2078. (k) Huang, J.-Z.; Jie, X.-K.; Wei, K.; Zhang, H.;
Wang, M.-C.; Yang, Y.-R. Synlett 2013, 24, 1303. (l) Li, Z.; Zhang, S.; Wu,
S.;Shen, X.;Zou, L.;Wang, F.;Li, X.;Peng, F.;Zhang, H.;Shao, Z. Angew.
Chem., Int. Ed. 2013, 52, 4117. (m) Nidhiry, J. E.; Prasad, K. R.
Tetrahedron2013,69, 5525. (n)Zhao, S.;Andrade, R.B. J. Am. Chem. Soc.
013, 135, 13334.
4) Kamisaki, H.; Nanjo, T.; Tsukano, C.; Takemoto, Y. Chem. - Eur. J.
011, 17, 626.
5) Frei, R.;Staedler, D.; Raja, A.; Franke, R.; Sasse, F.; Gerber-Lemaire,
S.; Waser, J. Angew. Chem., Int. Ed. 2013, 52, 13373.
6) For recent reviews on ynamide chemistry, see: (a) DeKorver, K. A.;
Li, H.; Lohse, A. G.; Hayashi, R.; Lu, Z.; Zhang, Y.; Hsung, R. P. Chem.
graphicdataforthispaper. Thesedatacanbeobtainedfreeofchargefrom
The Cambridge Crystallographic Data Centre.
́
ard, K. C.;
(
12) Yu, H.-Z.; Jiang, Y.-Y.; Fu, Y.; Liu, L. J. Am. Chem. Soc. 2010, 132,
8078.
13) Zhang, S.-L.; Liu, L.; Fu, Y.; Guo, Q.-X. Organometallics 2007, 26,
546.
14) Jones, G. O.; Liu, P.; Houk, K. N.; Buchwald, S. L. J. Am. Chem. Soc.
010, 132, 6205.
15) Fabre, I.; Perego, L. A.;Berges
M. Eur. J. Org. Chem. 2016, 2016, 5887.
16) Lefevre, G.; Franc, G.; Adamo, C.; Jutand, A.; Ciofini, I.
Organometallics 2012, 31, 914.
1
(
4
(
6
2
(
̀
, J.; Ciofini, I.; Grimaud, L.; Taillefer,
(
̀
2
(
2
(
(
(
(
17) Tsipis, A. C. Coord. Chem. Rev. 2014, 272, 1.
18) Guo, H.; Xue, Y. J. Theor. Comput. Chem. 2012, 11, 1135.
19) Fraile, J. M.; García, J. I.; Martínez-Merino, V.; Mayoral, J. A.;
Salvatella, L. J. Am. Chem. Soc. 2001, 123, 7616.
(
(
20) Franc, G.; Jutand, A. Dalton Trans. 2010, 39, 7873.
21) Villeneuve, K.; Riddell, N.; Tam, W. Tetrahedron 2006, 62, 3823.
(
D
Org. Lett. XXXX, XXX, XXX−XXX