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L. Zhang, J. Am. Chem. Soc., 2006, 128, 8414; (c) A. Buzas and
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A. V. Kel’in and V. Gevorgyan, Angew. Chem., Int. Ed., 2004,
43, 2280.
4 L. Peng, X. Zhang, S. Zhang and J. Wang, J. Org. Chem., 2007, 72,
1192.
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Scheme 1 Possible reaction pathways.
6 A. T. Blomquist, L. H. Liu and J. C. Bohrer, J. Am. Chem. Soc.,
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Commun., 2008, 2929; (b) I. Erden, W. Cao, M. Price and
M. Colton, Tetrahedron, 2008, 64, 5497; (c) M. Ogasawara,
A. Okada, K. Nakajima and T. Takahashi, Org. Lett., 2009, 11,
177.
8 S. Harusawa, H. Moriyama, N. Kase, H. Ohishi, R. Yoneda and
T. Kurihara, Tetrahedron, 1995, 51, 6475.
9 M. A. Hofmann, U. Bergstraßer, G. J. Reiß, L. Nyulaszi and
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N. Kamigata, J. Org. Chem., 2000, 65, 1721.
12 Crystal data for 2a: [C18H16S2], M = 296.43, monoclinic, space
group P21/n, a = 10.491(2), b = 8.7754(18), c = 17.309(4) A,
b = 104.25(3), V = 1544.4(5) A3, Z = 4, T = 293(2) K, m =
0.332 mmꢂ1, reflections collected/unique 10 549/3511 [R(int) =
0.0313]. Final R indices [I 4 2 s(I)] R1 = 0.0404. wR2 = 0.0946.
CCDC 720411.
13 For 4: [C18H16O4S2], M = 360.43, monoclinic, space group P21/c,
a = 11.306(2), b = 10.818(2), c = 14.594(3) A, b = 111.03(3),
V = 1666.1(6) A3, Z = 4, T = 293(2) K, reflections collected/
unique 15234/3821 [R(int) = 0.0466]. Final R indices [I 4 2s(I)]
R1 = 0.0384. wR2 = 0.0947. CCDC 720412.
calculation, they have suggested a mechanism of double
1,2-acetoxy migrations that accounts for the formal 1,3-migration
of the acetoxy group. In view of this study, we consider that
double 1,2-sulfur migrations are more likely in our reaction
(pathway A), although further investigation is needed to
unambiguously differentiate the two reaction pathways.
In conclusion, we have reported a novel rearrangement of
propargylic dithioacetals catalyzed by Au(PPh3)Cl/AgSbF6,
which affords 1,3-bisthio-substituted cyclic allenes in good
yields. To the best of our knowledge, this is the first example
of 8-membered 1,3-bisthio-substituted cyclic allenes. The
remarkable stability of the cyclic allenes allows us to inspect
their structure in detail, which adds useful information on the
family of hetero atom substituted cyclic allenes.
The project is generously supported by NSFC (Grant No.
20832002, 20772003, 20821062), the Ministry of Education of
China, and the National Basic Research Program of China
(973 Program, No. 2009CB825300).
Notes and references
1 For recent reviews, see: (a) S. Ma, S. Yu and Z. Gu, Angew. Chem.,
Int. Ed., 2006, 45, 200; (b) A. S. K. Hashmi and C. J. Hutchings,
Angew. Chem., Int. Ed., 2006, 45, 7896; (c) E. Jimenez-Nunez and
A. M. Echavarren, Chem. Commun., 2007, 333; (d) A. Furstner and
P. W. Davies, Angew. Chem., Int. Ed., 2007, 46, 3410; (e) A. S.
14 For a study on 1,2-sulfur shifts in Rh(II) carbene reaction, see:
F. Xu, W. Shi and J. Wang, J. Org. Chem., 2005, 70, 4191.
15 A. Correa, N. Marion, L. Fensterbank, M. Malacria, S. P. Nolan
and L. Cavallo, Angew. Chem., Int. Ed., 2008, 47, 718.
ꢁc
This journal is The Royal Society of Chemistry 2009
Chem. Commun., 2009, 2535–2537 | 2537