Optically active cyclic diaryl(alkoxy)sulfonium salts with intramolecular S···O interaction: synthesis, absolute configuration and stereoselective hydrolysis
Optically active cyclic sulfonium salts {( S)-(−)-1-[2′-(methoxycarbonyl)phenyl]-3 H-2,1-benzoxathiol-1-ium tetrafluoroborate ( S)-(−)- 2, ( R)-(−)-1-[8′-(methoxycarbonyl)-1′-naphthyl]-3 H-2,1-benzoxathiol-1-ium tetrafluoroborate ( R)-(−)- 4 and ( R)-(−)-1-[2′-(methoxycarbonyl)phenyl]-3 H-2,1-naphth...
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Published in | Tetrahedron: asymmetry Vol. 11; no. 6; pp. 1303 - 1312 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier Ltd
07.04.2000
|
Online Access | Get full text |
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Summary: | Optically active cyclic sulfonium salts {(
S)-(−)-1-[2′-(methoxycarbonyl)phenyl]-3
H-2,1-benzoxathiol-1-ium tetrafluoroborate (
S)-(−)-
2, (
R)-(−)-1-[8′-(methoxycarbonyl)-1′-naphthyl]-3
H-2,1-benzoxathiol-1-ium tetrafluoroborate (
R)-(−)-
4 and (
R)-(−)-1-[2′-(methoxycarbonyl)phenyl]-3
H-2,1-naphtho[1,8-
d,
e]-oxathiin-1-ium tetrafluoroborate (
R)-(−)-
6} were prepared from optically active diaryl(acyloxy)(alkoxy)spiro-λ
4-sulfanes (
R)-(+)-
1, (
S)-(−)-
3 and (
S)-(+)-
5, respectively. The molecular structures determined by
1H and
13C NMR measurements can be described with spiro-λ
4-sulfane-like trigonal bipyramidal geometry about the central sulfur owing to the S···O(carbonyl) intramolecular interaction in the axial position. The stereochemistry of the hydrolysis reactions of sulfonium salts
2,
4,
6 and spiro-λ
4-sulfanes
1,
3,
5 depending on pH is discussed in detail. |
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ISSN: | 0957-4166 1362-511X |
DOI: | 10.1016/S0957-4166(00)00064-1 |