The first lateral functionalization of calix[4]arenes by a homologous anionic ortho-Fries rearrangement

O. Middel, Zoltan Greff, Nick J. Taylor, Willem Verboom, David Reinhoudt, Victor Snieckus

Research output: Contribution to journalArticleAcademicpeer-review

65 Citations (Scopus)

Abstract

Treatment of calix[4]arene bis-O-carbamates 4a,b-6a,b with LDA in THF results in the regio- and stereoselective introduction of both axial and equatorial carboxamide groups at the methylene bridges via a homologous anionic ortho-Fries rearrangement to give 7-16. The stereochemical outcome of the rearrangement is dependent on the reaction conditions and the conformation of the starting material. Stereochemical and structural proof has been secured by the X-ray crystal structure of calix[4]arene 10 having only one equatorial carboxamide moiety. The use of this novel class of methylene bridge-functionalized calix[4]arenes is illustrated by the formation of bis--lactone 19, while the enhanced acidity of the remaining hydroxyl groups, owing to the presence of axial carboxamide groups at the methine bridges, followed from the easy propylation of bisrearranged calix[4]arene 7.
Original languageUndefined
Pages (from-to)667-675
JournalJournal of organic chemistry
Volume65
Issue number3
DOIs
Publication statusPublished - 2000

Keywords

  • METIS-106265
  • IR-11643

Cite this

@article{202fb36c52ac4992ab5034e2022baef7,
title = "The first lateral functionalization of calix[4]arenes by a homologous anionic ortho-Fries rearrangement",
abstract = "Treatment of calix[4]arene bis-O-carbamates 4a,b-6a,b with LDA in THF results in the regio- and stereoselective introduction of both axial and equatorial carboxamide groups at the methylene bridges via a homologous anionic ortho-Fries rearrangement to give 7-16. The stereochemical outcome of the rearrangement is dependent on the reaction conditions and the conformation of the starting material. Stereochemical and structural proof has been secured by the X-ray crystal structure of calix[4]arene 10 having only one equatorial carboxamide moiety. The use of this novel class of methylene bridge-functionalized calix[4]arenes is illustrated by the formation of bis--lactone 19, while the enhanced acidity of the remaining hydroxyl groups, owing to the presence of axial carboxamide groups at the methine bridges, followed from the easy propylation of bisrearranged calix[4]arene 7.",
keywords = "METIS-106265, IR-11643",
author = "O. Middel and Zoltan Greff and Taylor, {Nick J.} and Willem Verboom and David Reinhoudt and Victor Snieckus",
year = "2000",
doi = "10.1021/jo990976y",
language = "Undefined",
volume = "65",
pages = "667--675",
journal = "Journal of organic chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "3",

}

The first lateral functionalization of calix[4]arenes by a homologous anionic ortho-Fries rearrangement. / Middel, O.; Greff, Zoltan; Taylor, Nick J.; Verboom, Willem; Reinhoudt, David; Snieckus, Victor.

In: Journal of organic chemistry, Vol. 65, No. 3, 2000, p. 667-675.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - The first lateral functionalization of calix[4]arenes by a homologous anionic ortho-Fries rearrangement

AU - Middel, O.

AU - Greff, Zoltan

AU - Taylor, Nick J.

AU - Verboom, Willem

AU - Reinhoudt, David

AU - Snieckus, Victor

PY - 2000

Y1 - 2000

N2 - Treatment of calix[4]arene bis-O-carbamates 4a,b-6a,b with LDA in THF results in the regio- and stereoselective introduction of both axial and equatorial carboxamide groups at the methylene bridges via a homologous anionic ortho-Fries rearrangement to give 7-16. The stereochemical outcome of the rearrangement is dependent on the reaction conditions and the conformation of the starting material. Stereochemical and structural proof has been secured by the X-ray crystal structure of calix[4]arene 10 having only one equatorial carboxamide moiety. The use of this novel class of methylene bridge-functionalized calix[4]arenes is illustrated by the formation of bis--lactone 19, while the enhanced acidity of the remaining hydroxyl groups, owing to the presence of axial carboxamide groups at the methine bridges, followed from the easy propylation of bisrearranged calix[4]arene 7.

AB - Treatment of calix[4]arene bis-O-carbamates 4a,b-6a,b with LDA in THF results in the regio- and stereoselective introduction of both axial and equatorial carboxamide groups at the methylene bridges via a homologous anionic ortho-Fries rearrangement to give 7-16. The stereochemical outcome of the rearrangement is dependent on the reaction conditions and the conformation of the starting material. Stereochemical and structural proof has been secured by the X-ray crystal structure of calix[4]arene 10 having only one equatorial carboxamide moiety. The use of this novel class of methylene bridge-functionalized calix[4]arenes is illustrated by the formation of bis--lactone 19, while the enhanced acidity of the remaining hydroxyl groups, owing to the presence of axial carboxamide groups at the methine bridges, followed from the easy propylation of bisrearranged calix[4]arene 7.

KW - METIS-106265

KW - IR-11643

U2 - 10.1021/jo990976y

DO - 10.1021/jo990976y

M3 - Article

VL - 65

SP - 667

EP - 675

JO - Journal of organic chemistry

JF - Journal of organic chemistry

SN - 0022-3263

IS - 3

ER -