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Journal Name
ARTICLE
M. Kitajima and H. Takayama, Org. Biomol. Chem., 2015, 13
identical spectroscopic properties in all respects to the natural
product.
7762; (k) W. W. Felix, T. F. Hartrampf and D. Trauner, Angew.
DOI: 10.1039/C8CC01626G
Chem. Int. Ed., 2017, 56, 893; (l) W. W. Felix, T. F. Hartrampf
and D. Trauner, J. Org. Chem., 2017, 82, 8206; (m) L. Meng, J.
Org. Chem., 2016, 81, 7784; (n) K. Hiroya, Y. Suwa, Y.
Ichihashi, K. Inamoto and T. Doi, J. Org. Chem., 2011, 76
,
4522; (o) X. J. Liu and S. L. You, Angew. Chem., Int. Ed., 2017,
56, 1; (p) J. E. DeLorbe, M. D. Lotz and S. F. Martin, Org. Lett.,
2010, 12, 1576; (q) S. T. Staben, J. J. Kennedy-Smith, D.
Huang, B. K. Corkey, R. L. LaLonde and F. D. Toste, Angew.
Chem., Int. Ed., 2006, 45, 5991; (r) T. Xu, X. L. Luo and Y. Yang,
Tetrahedron Lett., 2013, 54, 2858.
7
(a) M. Toyota, A. llangovan, R. Okamoto, T. Masaki, M.
Arakawa and M. Ihara, Org. Lett., 2002, 4, 4293; (b) A. S.
Kende, B. Roth, P. J. Sanfilippo and T. J. Blacklock, J. Am.
Chem. Soc., 1982, 104, 5808; (c) A. S. Kende, B. Roth and P. J.
Sanfilippo, J. Am. Chem. Soc., 1982, 104, 1784.
S. Kumar, P. D. Thornton, T. O. Painter, P. Jain, J. Downard, J.
T. Douglas and C. Santini, J. Org. Chem., 2013, 78, 6529.
8
9
D. Caine, K. Proter and R. A. Cassell, J. Org. Chem., 1984, 49
2647.
,
Scheme 5. Total synthesis of (+)-lycopladine A (2).
10 B. Guillaume, St. O. Miguel and B. C. Andre, Org. Lett., 2008,
10, 5497.
11 T. Nishimura, A. K. Unni, S. Yokoshima, T. Fukuyama, J. Am.
Chem. Soc., 2013, 135, 3243.
12 R. K. Alan, M. Roman, V. S. Christian and F. G. Mikhail, J. Org.
Chem., 1994, 59, 2740.
In summary, by using a divergent strategy we have developed a
concise, asymmetric total synthesis of both (–)-lycoposerramine-R
(1) and (+)-lycopladine A (2) from known phenylsulfide 1 in 9 and 7
steps, respectively. The key features of the current synthesis
include a palladium-catalyzed cycloalkenylation of silyl enol ether 5
for assembling the 6,5-fused hydrindane and generating
a
quaternary carbon center in one step. The application of these
synthetic studies to an enantioselective synthesis of the related
fawcettimine-type alkaloid 3 will be reported in due course.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China for the financial support of this work (Grant #21372221
and #21572228).
Notes and references
1
2
X. Ma and D. R. Gang, Nat. Prod. Rep., 2004, 21, 752.
Y. Hirasawa, J. Kobayashi and H. Morita, Heterocycles., 2009,
77, 679.
P. Siengalewicz, J. Mulzer and U. Rinner, In The Alkaloids:
Chemistry and Biology; Hans-Joachim, K., Ed.; Academic
Press: New York, 2013; Vol. 72, p 1.
3
4
5
6
K. Katakawa, N. Kogure, M. Kitajima and H. Takayama, Helv.
Chim. Acta., 2009, 92, 445.
K. I. Ishiuchi, T. Kubota, H. Morita and J. I. Kobayashi,
Tetrahedron Lett., 2006, 47, 3287.
For selected recent examples of total synthesis of
lycopodium alkaloids, see: (a) B. K. Hong, H. H. Li, J. B. Wu, J.
Zhang and X. G. Lei, Angew. Chem., Int. Ed. 2015, 54, 1011; (b)
P. S. Chauhan, J. R. Sacher and S. M. Weinreb, Org. Lett. 2015,
17, 806; (c) K. W. Lin, B. Ananthan, S. F. Tseng and T. H. Yan,
Org. Lett., 2015, 17, 3938; (d) C. Bosch, B. Fiser, E. Gomez-
Bengoa, B. Bradshaw and J. Bonjoch, Org. Lett. 2015, 17
5084; (e) R. A. Samame, C. M. Owens and S. D. Rychnovsky,
Chem. Sci., 2016, , 188; (f) B. M. Williams and D. Trauner,
,
7
Angew. Chem., Int. Ed., 2016, 55, 2191; (g) Y. Ochi, S.
Yokoshima and T. Fukuyama, Org. Lett., 2016, 18, 1494; (h) V.
Bisai and R. Sarpong, Org. Lett., 2010, 12, 2552; (i) H. Ishida,
S. Kimura, N. Kogure, M. Kitajima and H. Takayama,
Tetrahedron, 2015, 71, 51; (j) H. Ishida, S. Kimura, N. Kogure,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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