Synthesis of an inherently chiral O,O′-bridged thiacalix[4] crowncarboxylic acid and its application to a chiral solvating agent

Fumitaka Narumi; Tetsutaro Hattori; Nobuji Matsumura; Toru Onodera; Hiroshi Katagiri; Chizuko Kabuto; Hiroshi Kameyama; Sotaro Miyano

doi:10.1016/j.tet.2004.06.074

Synthesis of an inherently chiral O,O′-bridged thiacalix[4] crowncarboxylic acid and its application to a chiral solvating agent

Fumitaka Narumi, Tetsutaro Hattori, Nobuji Matsumura, Toru Onodera, Hiroshi Katagiri, Chizuko Kabuto, Hiroshi Kameyama, Sotaro Miyano

ENG - Biomolecular Engineering

Research output: Contribution to journal › Article › peer-review

57 Citations (Scopus)

Abstract

Treatment of readily available O,O′-1,1,3,3-tetraisopropyldisiloxane- 1,3-diyl-bridged p-tert-butylthiacalix[4]arene (1) with tri(ethylene glycol) di-p-tosylate and subsequent desilylation gave O,O′-bridged thiacalix[4]crown 3 in an excellent yield. Mono-O-alkylation of 3 with ethyl bromoacetate, followed by optical resolution by chiral HPLC, and subsequent hydrolysis of the ester moiety gave inherently chiral O,O′-bridged thiacalix[4]crowncarboxylic acid (+)-6, which clearly discriminated enantiomeric primary amines, as well as amino esters, by ¹H NMR spectroscopy.

Original language	English
Pages (from-to)	7827-7833
Number of pages	7
Journal	Tetrahedron
Volume	60
Issue number	36
DOIs	https://doi.org/10.1016/j.tet.2004.06.074
Publication status	Published - 2004 Aug 30

Keywords

Calixarene
Calixcrown
Chiral recognition
Inherently chiral

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title = "Synthesis of an inherently chiral O,O′-bridged thiacalix[4] crowncarboxylic acid and its application to a chiral solvating agent",

abstract = "Treatment of readily available O,O′-1,1,3,3-tetraisopropyldisiloxane- 1,3-diyl-bridged p-tert-butylthiacalix[4]arene (1) with tri(ethylene glycol) di-p-tosylate and subsequent desilylation gave O,O′-bridged thiacalix[4]crown 3 in an excellent yield. Mono-O-alkylation of 3 with ethyl bromoacetate, followed by optical resolution by chiral HPLC, and subsequent hydrolysis of the ester moiety gave inherently chiral O,O′-bridged thiacalix[4]crowncarboxylic acid (+)-6, which clearly discriminated enantiomeric primary amines, as well as amino esters, by 1H NMR spectroscopy.",

keywords = "Calixarene, Calixcrown, Chiral recognition, Inherently chiral",

author = "Fumitaka Narumi and Tetsutaro Hattori and Nobuji Matsumura and Toru Onodera and Hiroshi Katagiri and Chizuko Kabuto and Hiroshi Kameyama and Sotaro Miyano",

note = "Funding Information: This work was supported in part by the Proposal-Based New Industry Creative Type Technology R and D Promotion Program from NEDO and a Grant-in-Aid for Scientific Research on Priority Areas (No. 14044009) from the Ministry of Education and Technology, Japan.",

year = "2004",

month = aug,

day = "30",

doi = "10.1016/j.tet.2004.06.074",

language = "English",

volume = "60",

pages = "7827--7833",

journal = "Tetrahedron",

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TY - JOUR

T1 - Synthesis of an inherently chiral O,O′-bridged thiacalix[4] crowncarboxylic acid and its application to a chiral solvating agent

AU - Narumi, Fumitaka

AU - Hattori, Tetsutaro

AU - Matsumura, Nobuji

AU - Onodera, Toru

AU - Katagiri, Hiroshi

AU - Kabuto, Chizuko

AU - Kameyama, Hiroshi

AU - Miyano, Sotaro

N1 - Funding Information: This work was supported in part by the Proposal-Based New Industry Creative Type Technology R and D Promotion Program from NEDO and a Grant-in-Aid for Scientific Research on Priority Areas (No. 14044009) from the Ministry of Education and Technology, Japan.

PY - 2004/8/30

Y1 - 2004/8/30

N2 - Treatment of readily available O,O′-1,1,3,3-tetraisopropyldisiloxane- 1,3-diyl-bridged p-tert-butylthiacalix[4]arene (1) with tri(ethylene glycol) di-p-tosylate and subsequent desilylation gave O,O′-bridged thiacalix[4]crown 3 in an excellent yield. Mono-O-alkylation of 3 with ethyl bromoacetate, followed by optical resolution by chiral HPLC, and subsequent hydrolysis of the ester moiety gave inherently chiral O,O′-bridged thiacalix[4]crowncarboxylic acid (+)-6, which clearly discriminated enantiomeric primary amines, as well as amino esters, by 1H NMR spectroscopy.

AB - Treatment of readily available O,O′-1,1,3,3-tetraisopropyldisiloxane- 1,3-diyl-bridged p-tert-butylthiacalix[4]arene (1) with tri(ethylene glycol) di-p-tosylate and subsequent desilylation gave O,O′-bridged thiacalix[4]crown 3 in an excellent yield. Mono-O-alkylation of 3 with ethyl bromoacetate, followed by optical resolution by chiral HPLC, and subsequent hydrolysis of the ester moiety gave inherently chiral O,O′-bridged thiacalix[4]crowncarboxylic acid (+)-6, which clearly discriminated enantiomeric primary amines, as well as amino esters, by 1H NMR spectroscopy.

KW - Calixarene

KW - Calixcrown

KW - Chiral recognition

KW - Inherently chiral

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U2 - 10.1016/j.tet.2004.06.074

DO - 10.1016/j.tet.2004.06.074

M3 - Article

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SN - 0040-4020

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JO - Tetrahedron

JF - Tetrahedron

IS - 36

ER -

Synthesis of an inherently chiral O,O′-bridged thiacalix[4] crowncarboxylic acid and its application to a chiral solvating agent

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Keywords

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