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Syntheses of inherently chiral monosulfinyltrithiacalix[4]arenes by the oxidation of one of the bridging sulfurs of a tetrathiacalix[4]arene fixed in the 1,3‐alternate conformation
Author(s) -
Morohashi Naoya,
Naito Ryoichiro,
Iki Nobuhiko,
Miyano Sotaro
Publication year - 2002
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1560/vqjk-0q49-hrwr-e2f1
Subject(s) - chemistry , diastereomer , yield (engineering) , ether , calixarene , medicinal chemistry , derivative (finance) , organic chemistry , stereochemistry , polymer chemistry , molecule , materials science , metallurgy , economics , financial economics
A new synthetic strategy for the construction of an inherently chiral, sulfur‐bridged calix[4]arene molecular framework was presented by oxidation of one of the four epithio bonds of a tetrathiacalix[4]arene derivative of 1,3‐alternate conformation: Tetra(carboxymethyl) ether of p‐tert ‐butyltetrathiacalix[4]arene of 1,3‐alternate conformation ( 7 ) was converted to the tetra( l ‐menthoxycarbonylmethyl) ether ( 8 ). Oxidation of the tetra l ‐menthyl ester 8 by treatment with NaBO 3 (1.1 molar equiv.) afforded a pair of diastereomers of the monosulfinyl derivatives ( 9 ) in 58% yield, which were readily separable by silica‐gel column chromatography. Removal of the l ‐menthyl moieties followed by methyl esterification gave enantiomerically pure samples of inherently chiral (‐)‐ and (+)‐monosulfinyltrithiacalix[4]arene derivatives ((‐) ‐10 and (+) ‐10 ) in 62 and 56% yield, respectively.