Tetracyanoanthraquinodimethanes with a chiral amide group

Preparation, properties, and charge-transfer photochirogenetic reaction with 1,2-dianisylacenaphthene-1,2-diol

Takanori Suzuki, Koji Ichioka, Hiroki Higuchi, Hidetoshi Kawai, Kenshu Fujiwara, Masakazu Ohkita, Takashi Tsuji, Yasutake Takahashi

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

A series of butterfly-shaped tetracyanoanthraquinodimethanes (TCNAQs) with a chiral amide auxiliary 1a-f were prepared from the corresponding anthraquinones. They are stronger acceptors than the unsubstituted derivative and undergo one-wave two-electron reduction. They form weak electron-donor- acceptor (EDA) complexes with the title pinacol 2. Upon charge-transfer excitation of these complexes, dihydro-TCNAQs 3 and 1,8-dianisoylnaphthalene 4 were efficiently formed, the latter of which is the product of a retropinacol reaction via 2+.. Partial enantiodifferentiation of rac-2 was realized during the photoreactions with 2-[(R)-1-phenylethylcarbamoyl]-TCNAQ 1a in CD3CN. Thus, optically active (S,S)-(+)-pinacol 2 (12.3% ee at 54% conversion; 21.5% ee at 70% conversion) was recovered from the photolyzates. This reaction represents a new and rare example of the pseudokinetic resolution of ieri-alcohol accompanied by C-C bond fission. Significant differences in the association constants for the diastereomeric EDA complexes are responsible for the observed enantiodifferentiation.

Original languageEnglish
Pages (from-to)5592-5598
Number of pages7
JournalJournal of Organic Chemistry
Volume70
Issue number14
DOIs
Publication statusPublished - Jul 8 2005

Fingerprint

Amides
Charge transfer
Electrons
Anthraquinones
Alcohols
Association reactions
Derivatives
tetracyanoanthraquinodimethane

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Tetracyanoanthraquinodimethanes with a chiral amide group : Preparation, properties, and charge-transfer photochirogenetic reaction with 1,2-dianisylacenaphthene-1,2-diol. / Suzuki, Takanori; Ichioka, Koji; Higuchi, Hiroki; Kawai, Hidetoshi; Fujiwara, Kenshu; Ohkita, Masakazu; Tsuji, Takashi; Takahashi, Yasutake.

In: Journal of Organic Chemistry, Vol. 70, No. 14, 08.07.2005, p. 5592-5598.

Research output: Contribution to journalArticle

Suzuki, Takanori ; Ichioka, Koji ; Higuchi, Hiroki ; Kawai, Hidetoshi ; Fujiwara, Kenshu ; Ohkita, Masakazu ; Tsuji, Takashi ; Takahashi, Yasutake. / Tetracyanoanthraquinodimethanes with a chiral amide group : Preparation, properties, and charge-transfer photochirogenetic reaction with 1,2-dianisylacenaphthene-1,2-diol. In: Journal of Organic Chemistry. 2005 ; Vol. 70, No. 14. pp. 5592-5598.
@article{a6d20c4e6cfa46e28ae9a16162f117ca,
title = "Tetracyanoanthraquinodimethanes with a chiral amide group: Preparation, properties, and charge-transfer photochirogenetic reaction with 1,2-dianisylacenaphthene-1,2-diol",
abstract = "A series of butterfly-shaped tetracyanoanthraquinodimethanes (TCNAQs) with a chiral amide auxiliary 1a-f were prepared from the corresponding anthraquinones. They are stronger acceptors than the unsubstituted derivative and undergo one-wave two-electron reduction. They form weak electron-donor- acceptor (EDA) complexes with the title pinacol 2. Upon charge-transfer excitation of these complexes, dihydro-TCNAQs 3 and 1,8-dianisoylnaphthalene 4 were efficiently formed, the latter of which is the product of a retropinacol reaction via 2+.. Partial enantiodifferentiation of rac-2 was realized during the photoreactions with 2-[(R)-1-phenylethylcarbamoyl]-TCNAQ 1a in CD3CN. Thus, optically active (S,S)-(+)-pinacol 2 (12.3{\%} ee at 54{\%} conversion; 21.5{\%} ee at 70{\%} conversion) was recovered from the photolyzates. This reaction represents a new and rare example of the pseudokinetic resolution of ieri-alcohol accompanied by C-C bond fission. Significant differences in the association constants for the diastereomeric EDA complexes are responsible for the observed enantiodifferentiation.",
author = "Takanori Suzuki and Koji Ichioka and Hiroki Higuchi and Hidetoshi Kawai and Kenshu Fujiwara and Masakazu Ohkita and Takashi Tsuji and Yasutake Takahashi",
year = "2005",
month = "7",
day = "8",
doi = "10.1021/jo0505324",
language = "English",
volume = "70",
pages = "5592--5598",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Tetracyanoanthraquinodimethanes with a chiral amide group

T2 - Preparation, properties, and charge-transfer photochirogenetic reaction with 1,2-dianisylacenaphthene-1,2-diol

AU - Suzuki, Takanori

AU - Ichioka, Koji

AU - Higuchi, Hiroki

AU - Kawai, Hidetoshi

AU - Fujiwara, Kenshu

AU - Ohkita, Masakazu

AU - Tsuji, Takashi

AU - Takahashi, Yasutake

PY - 2005/7/8

Y1 - 2005/7/8

N2 - A series of butterfly-shaped tetracyanoanthraquinodimethanes (TCNAQs) with a chiral amide auxiliary 1a-f were prepared from the corresponding anthraquinones. They are stronger acceptors than the unsubstituted derivative and undergo one-wave two-electron reduction. They form weak electron-donor- acceptor (EDA) complexes with the title pinacol 2. Upon charge-transfer excitation of these complexes, dihydro-TCNAQs 3 and 1,8-dianisoylnaphthalene 4 were efficiently formed, the latter of which is the product of a retropinacol reaction via 2+.. Partial enantiodifferentiation of rac-2 was realized during the photoreactions with 2-[(R)-1-phenylethylcarbamoyl]-TCNAQ 1a in CD3CN. Thus, optically active (S,S)-(+)-pinacol 2 (12.3% ee at 54% conversion; 21.5% ee at 70% conversion) was recovered from the photolyzates. This reaction represents a new and rare example of the pseudokinetic resolution of ieri-alcohol accompanied by C-C bond fission. Significant differences in the association constants for the diastereomeric EDA complexes are responsible for the observed enantiodifferentiation.

AB - A series of butterfly-shaped tetracyanoanthraquinodimethanes (TCNAQs) with a chiral amide auxiliary 1a-f were prepared from the corresponding anthraquinones. They are stronger acceptors than the unsubstituted derivative and undergo one-wave two-electron reduction. They form weak electron-donor- acceptor (EDA) complexes with the title pinacol 2. Upon charge-transfer excitation of these complexes, dihydro-TCNAQs 3 and 1,8-dianisoylnaphthalene 4 were efficiently formed, the latter of which is the product of a retropinacol reaction via 2+.. Partial enantiodifferentiation of rac-2 was realized during the photoreactions with 2-[(R)-1-phenylethylcarbamoyl]-TCNAQ 1a in CD3CN. Thus, optically active (S,S)-(+)-pinacol 2 (12.3% ee at 54% conversion; 21.5% ee at 70% conversion) was recovered from the photolyzates. This reaction represents a new and rare example of the pseudokinetic resolution of ieri-alcohol accompanied by C-C bond fission. Significant differences in the association constants for the diastereomeric EDA complexes are responsible for the observed enantiodifferentiation.

UR - http://www.scopus.com/inward/record.url?scp=22144452180&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=22144452180&partnerID=8YFLogxK

U2 - 10.1021/jo0505324

DO - 10.1021/jo0505324

M3 - Article

VL - 70

SP - 5592

EP - 5598

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 14

ER -