Synthesis and Conformational Analysis of Syn-Dithia[3.3][2,4]Thiazolophane and Syn-Dithia[3.3]([1,4]Phenyl[2,4]Thiazolophane) †

Abstract

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.

Keywords

cyclophanes thiazoles DNMR conformational mobility

References

(a) Newkome

G.R.

, Sauer

J. D.

, Roper

J. M.

, Hager

D. C.

, Chem. Rev., 1977, 73, 523; (b) R. H. Mitchell, Heterocycles, 1978, 11, 563; (c) Keehn

P. M.

, and Rosenfeld

S. 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.

(a) Mashraqui

S.H.

, and Keehn

P. 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.

(a) Mashraqui

S.H.

, and Keehn

P. 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.

(a) Ostubo

, and Boekelheide

, Tetrahedron Lett., 1970, 11, 1197.

(a) Vögtle

, and Schunder

, 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.

(a) Mashraqui

S.H.

, and Nivalkar

K. 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.

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.

Mukhina

M.V.

, and Postovskii

I. Ya.

, Khim. Geterotsikl. Soedin., Akad. Nauk Latv., SSR. 1965, 792 (CA, 1966, 64, 9712).

(a) Hantzsch

, and Weber

H. J.

, Berichte, 1887, 20, 3118; (b) G. Marzoni, J. Heterocycl. Chem., 1986, 23, 577.

10.

Case

F.H.

, J. Am. Chem. Soc., 1925, 47, 1143.

11.

Vincent

E.J.

, Phan-Tan-Luu

, Metzger

, and Surzur

J.-M.

, Bull. Soc. Chim. France, 1966, 3524 (CA, 1967, 66, 64912u).