Synthesis of syn-dithia[3.3][2,4]thiazolophane 1 and syn-dithia[3.3]([1,4]phenyl[2,4]thiazolophane) 2 was accomplished via the stepwise construction of two thiapropylene (CH2SCH2) bridges. Dynamic 1H NMR analysis reveals the heterophanes 1 and 2 to be conformationally mobile on the NMR time scale down to −55 °C.
(a) NewkomeG.R., SauerJ. D., RoperJ. M., HagerD. C., Chem. Rev., 1977, 73, 523; (b) R. H. Mitchell, Heterocycles, 1978, 11, 563; (c) KeehnP. M., and RosenfeldS. M. (ed) Cyclophanes. Academic Press, New York, Vols 1 and 2, 1983; (d) H. A. Staab, A. Feurer, C. Krieger and A. S. Kumar, Liebigs Ann., Recl. 1997, 11, 2321; (e) K. E. Keisha, W. Burkhardt, Y. Zhang and S. T. Diver, Org. Lett. 2000, 2, 3785; (f) E. Buncel, N. L. Mailloux, R. S. Brown, P. M. Kazmaier, and J. Dust, Tetrahedron Lett., 2001, 42, 3559.
2.
(a) MashraquiS.H., and KeehnP. M., J. Org. Chem., 1983, 48, 1341; (b) J. R. Fletcher and I. O. Sutherland, Chem. Commun. 1969, 1504; (c) C. Wong and W. W. Paudler, J. Org. Chem. 1974, 39, 2570; (d) H. Sasaki, R. Egi, K. Kawanishi, T. Kipagawa, and T. Shingu, Chem. Pharm. Bull. 1989, 37, 1176.
3.
(a) MashraquiS.H., and KeehnP. M., J. Am. Chem. Soc., 1982, 104, 4461; (b) I. Guilt, B. J. Price and I. O. Sutherland, Chem. Commun., 1967, 540; (c) S. A. Sherrod, R. L. deCosta, R. A. Barnes and V. Boekelheide, J. Am. Chem. Soc., 1974, 96, 1565.
4.
(a) OstuboT., and BoekelheideV., Tetrahedron Lett., 1970, 11, 1197.
5.
(a) VögtleF., and SchunderL., Chem. Ber., 1969, 102, 2677; (b) Y. H. Lai and A. H. Yap, J. Chem. Soc., Perkin Trans., 2 1993, 1373; (c) Y. Fukazawa, M. Aoyagi and S. Ito, Tetrahedron Lett. 1978, 19, 1067.
6.
(a) MashraquiS.H., and NivalkarK. R., Tetrahedron Lett.1997, 38, 4487; (b) S. H. Mashraqui, S. Kumar and K. R. Nivalkar, Heterocyclic Commun., 2001, 7, 74; (c) S. H. Mashraqui, M. M. Biswas and K. R. Nivalkar, Ind. J. Chem., 1996, 35B, 1031.
7.
For convenience, we denote the positional (connectivity) isomers by the terms syn (as here, with bridges connecting the same positions, in which the molecules have a potential plane of symmetry) and anti (potentially centrosymmetric, with bridges connecting opposite positions). The terms have no stereochemical connotation here. For the Baeyer system names – Chemical Abstracts usage – see the Experimental section.
8.
MukhinaM.V., and PostovskiiI. Ya., Khim. Geterotsikl. Soedin., Akad. Nauk Latv., SSR.1965, 792 (CA, 1966, 64, 9712).
9.
(a) HantzschA., and WeberH. J., Berichte, 1887, 20, 3118; (b) G. Marzoni, J. Heterocycl. Chem., 1986, 23, 577.
10.
CaseF.H., J. Am. Chem. Soc., 1925, 47, 1143.
11.
VincentE.J., Phan-Tan-LuuR., MetzgerJ., and SurzurJ.-M., Bull. Soc. Chim. France, 1966, 3524 (CA, 1967, 66, 64912u).
