catalyst18 to provide 1 in an 82% isolated yield. An X-ray
crystal structure of 1 was obtained (Scheme 3) that matched
the data previously reported.19–21
4490–4527; (b) A. Deiters and S. F. Martin, Chem. Rev., 2004, 104,
2199–2238.
11 For reviews on N-acyl iminium ion chemistry, see: (a) R. A. Pilli
and G. B. Rossi, in Science of Synthesis, ed. A. Padwa, Georg
Thieme Verlag, Stuttgart, 2004, vol. 27, pp. 375–439;
(b) B. E. Maryanoff, H.-C. Zhang, J. H. Cohen, I. J. Turchi and
C. A. Maryanoff, Chem. Rev., 2004, 104, 1431–1628.
12 X. Zhang, A. C. Schmitt and W. Jiang, Tetrahedron Lett., 2001, 42,
5335–5338.
13 G. Stork and K. Zhao, Tetrahedron Lett., 1989, 30, 2173–2174.
14 For a general synthesis of alkynes from aldehydes via the dehydro-
halogenation of (Z)-1-iodo-1-alkenes with TBAF, see: M. Beshai,
B. Dhudshia, R. Mills and A. N. Thadani, Tetrahedron Lett., 2008,
49, 6794–6796.
15 Suitable single crystals of 16 were covered with mineral oil and
mounted in the 173 K N2 stream of a Bruker AXS D8/APEX CCD
diffractometer equipped with an Mo Ka radiation source
(l = 0.71073 A). The structures were solved by direct methods
and refined using full matrix, least-squares on F2. Crystal data
In conclusion, a flexible synthesis of (ꢀ)-securinine (1) was
completed from trans-4-hydroxy-L-proline (7) in 18 steps and
16% overall isolated yield.22,23 The highlights of the synthesis
include an intramolecular Heck cyclization to complete the
tetracyclic skeleton, and the highly diastereoselective preparation
of the key spirocyclic a,b-unsaturated g-lactone intermediate. We
anticipate that the synthetic route can be readily modified to
access other Securinega alkaloids (e.g. norsecurinine), and are
currently working towards this goal.
This project was supported by research funding from the
National Science and Engineering Research Council (NSERC)
of Canada and the University of Windsor.
for 16: C10H15NO,
M = 165.23, orthorhombic, P212121,
a = 7.4042(10), b = 8.5718(11), c = 14.7778(19) A, V =
937.9(2) A3, Z = 4, Dcalc = 1.170 g cmꢀ3, m(Mo Ka) =
0.075 mmꢀ1. A total of 10 354 reflections were collected in the
range 5.50 o 2y o 55.00. Of these, 1266 were independent; for the
observed data, wR2 = 0.0964, R = 0.0377. See the ESI for
complete details regarding data collection, solution and refinement
of the structure. CCDC 703221w.
Notes and references
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3 For a recent review of the biological properties of 1, see: D. Raj
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(b) Russian Pharmacopeia, Ministry of Health of the USSR,
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17 For reviews on intramolecular Heck reactions, see: (a) J. T. Link,
Org. React. (N. Y.), 2002, 60, 157–534; (b) J. Tsuji Palladium
Reagents and Catalysts: New Perspectives for the 21st Century,
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Targets Heterocycl. Syst., 2005, 9, 281–310.
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19 Suitable single crystals of 1 were covered with mineral oil and
mounted in the 173 K N2 stream of a Bruker AXS D8/APEX CCD
diffractometer equipped with an Mo Ka radiation source (l =
0.71073 A). The structures were solved by direct methods and
refined using full matrix, least-squares on F2. Crystal data for 1:
C13H15NO2, M = 217.26, orthorhombic, P212121, a = 6.9876(10),
b = 9.3485(13), c = 16.411(2) A, V = 1072.0(3) A3, Z = 4,
Dcalc = 1.346 g cmꢀ3, m(Mo Ka) = 0.091 mmꢀ1. A total of 12 043
reflections were collected in the range 4.98 o 2y o 55.00. Of these,
1416 were independent; for the observed data, wR2 = 0.0866, R =
0.0372. See the ESI for complete details regarding data collection,
solution and refinement of the structure. CCDC 70322w.
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T. Honda, H. Namiki, K. Kaneda and H. Mizutani, Org. Lett.,
2004, 6, 87–89.
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ꢂc
This journal is The Royal Society of Chemistry 2009
Chem. Commun., 2009, 463–465 | 465