Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril

Asao Nakamura, Hiromi Irie, Shuhei Hara, Mai Sugawara, Shinji Yamada

研究成果: Article

20 引用 (Scopus)

抄録

Addition of HCl accelerated the photocyclodimerization of trans-4-styrylpyridine 1a in methanol and increased the yield of syn-head-to-tail (syn-HT) dimer 2a through the effect of cation-π interactions between the pyridinium ion of one molecule and the phenyl group of the other. We examined the photoirradiation products of derivatives of 1a having alkyl substituents on the phenyl group (1b-1f). The effect of the alkyl substituent on product distribution was rather limited for the photoreaction in MeOH solutions. However, the substituents had a distinct effect on the product distribution for the photoreaction of the inclusion complexes of hydrochloride salts of trans-4-styrylpyridines with cucurbit[8]uril in aqueous solutions. Introducing an alkyl group at the 2- or 3-position of the phenyl group completely shifted the major product from the syn-HT dimer to the syn-head-to-head (syn-HH) dimer. By adjusting the balance of host-guest interactions and cation-π interactions between guest molecules through systematic changes in the substituents on the phenyl ring of trans-4-styrylpyridine, we could change the orientation of the reactant molecules in the host cavity, resulting in a change of the major regioisomer of the photocyclodimerization products.

元の言語English
ページ(範囲)1496-1500
ページ数5
ジャーナルPhotochemical and Photobiological Sciences
10
発行部数9
DOI
出版物ステータスPublished - 2011 9

Fingerprint

Dimers
Molecules
Cations
products
dimers
Methanol
cations
molecules
Salts
Ions
Derivatives
hydrochlorides
interactions
methyl alcohol
adjusting
4-stilbazole
cucurbit(8)uril
inclusions
aqueous solutions
salts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

これを引用

Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril. / Nakamura, Asao; Irie, Hiromi; Hara, Shuhei; Sugawara, Mai; Yamada, Shinji.

:: Photochemical and Photobiological Sciences, 巻 10, 番号 9, 09.2011, p. 1496-1500.

研究成果: Article

Nakamura, Asao ; Irie, Hiromi ; Hara, Shuhei ; Sugawara, Mai ; Yamada, Shinji. / Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril. :: Photochemical and Photobiological Sciences. 2011 ; 巻 10, 番号 9. pp. 1496-1500.
@article{140b5f92e1744203ba1a9895c03cbfa0,
title = "Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril",
abstract = "Addition of HCl accelerated the photocyclodimerization of trans-4-styrylpyridine 1a in methanol and increased the yield of syn-head-to-tail (syn-HT) dimer 2a through the effect of cation-π interactions between the pyridinium ion of one molecule and the phenyl group of the other. We examined the photoirradiation products of derivatives of 1a having alkyl substituents on the phenyl group (1b-1f). The effect of the alkyl substituent on product distribution was rather limited for the photoreaction in MeOH solutions. However, the substituents had a distinct effect on the product distribution for the photoreaction of the inclusion complexes of hydrochloride salts of trans-4-styrylpyridines with cucurbit[8]uril in aqueous solutions. Introducing an alkyl group at the 2- or 3-position of the phenyl group completely shifted the major product from the syn-HT dimer to the syn-head-to-head (syn-HH) dimer. By adjusting the balance of host-guest interactions and cation-π interactions between guest molecules through systematic changes in the substituents on the phenyl ring of trans-4-styrylpyridine, we could change the orientation of the reactant molecules in the host cavity, resulting in a change of the major regioisomer of the photocyclodimerization products.",
author = "Asao Nakamura and Hiromi Irie and Shuhei Hara and Mai Sugawara and Shinji Yamada",
year = "2011",
month = "9",
doi = "10.1039/c1pp05079f",
language = "English",
volume = "10",
pages = "1496--1500",
journal = "Photochemical and Photobiological Sciences",
issn = "1474-905X",
publisher = "Royal Society of Chemistry",
number = "9",

}

TY - JOUR

T1 - Regiospecific [2 + 2] photocyclodimerization of trans-4-styrylpyridines templated by cucurbit[8]uril

AU - Nakamura, Asao

AU - Irie, Hiromi

AU - Hara, Shuhei

AU - Sugawara, Mai

AU - Yamada, Shinji

PY - 2011/9

Y1 - 2011/9

N2 - Addition of HCl accelerated the photocyclodimerization of trans-4-styrylpyridine 1a in methanol and increased the yield of syn-head-to-tail (syn-HT) dimer 2a through the effect of cation-π interactions between the pyridinium ion of one molecule and the phenyl group of the other. We examined the photoirradiation products of derivatives of 1a having alkyl substituents on the phenyl group (1b-1f). The effect of the alkyl substituent on product distribution was rather limited for the photoreaction in MeOH solutions. However, the substituents had a distinct effect on the product distribution for the photoreaction of the inclusion complexes of hydrochloride salts of trans-4-styrylpyridines with cucurbit[8]uril in aqueous solutions. Introducing an alkyl group at the 2- or 3-position of the phenyl group completely shifted the major product from the syn-HT dimer to the syn-head-to-head (syn-HH) dimer. By adjusting the balance of host-guest interactions and cation-π interactions between guest molecules through systematic changes in the substituents on the phenyl ring of trans-4-styrylpyridine, we could change the orientation of the reactant molecules in the host cavity, resulting in a change of the major regioisomer of the photocyclodimerization products.

AB - Addition of HCl accelerated the photocyclodimerization of trans-4-styrylpyridine 1a in methanol and increased the yield of syn-head-to-tail (syn-HT) dimer 2a through the effect of cation-π interactions between the pyridinium ion of one molecule and the phenyl group of the other. We examined the photoirradiation products of derivatives of 1a having alkyl substituents on the phenyl group (1b-1f). The effect of the alkyl substituent on product distribution was rather limited for the photoreaction in MeOH solutions. However, the substituents had a distinct effect on the product distribution for the photoreaction of the inclusion complexes of hydrochloride salts of trans-4-styrylpyridines with cucurbit[8]uril in aqueous solutions. Introducing an alkyl group at the 2- or 3-position of the phenyl group completely shifted the major product from the syn-HT dimer to the syn-head-to-head (syn-HH) dimer. By adjusting the balance of host-guest interactions and cation-π interactions between guest molecules through systematic changes in the substituents on the phenyl ring of trans-4-styrylpyridine, we could change the orientation of the reactant molecules in the host cavity, resulting in a change of the major regioisomer of the photocyclodimerization products.

UR - http://www.scopus.com/inward/record.url?scp=80052199467&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80052199467&partnerID=8YFLogxK

U2 - 10.1039/c1pp05079f

DO - 10.1039/c1pp05079f

M3 - Article

C2 - 21691651

AN - SCOPUS:80052199467

VL - 10

SP - 1496

EP - 1500

JO - Photochemical and Photobiological Sciences

JF - Photochemical and Photobiological Sciences

SN - 1474-905X

IS - 9

ER -