Tetraaryl-, Pentaaryl-, and Hexaaryl-1,4-dihydropyrrolo 3,2-b pyrroles: Synthesis and Optical Properties

M. Krzeszewski, B. Thorsted, J. Brewer, D. T. Gryko

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Efficient conditions for the synthesis of tetra-, penta-, and hexasubstituted derivatives of 1,4-dihydropyrrolo[3,2-b]pyrrole were developed. The tetraaryl derivatives were obtained in a novel one-pot reaction among aromatic aldehydes, aromatic amines, and butane-2,3-dione. After a thorough examination of various reaction parameters (solvent, acid, temperature) p-toluenesulfonic acid was identified as the crucial catalyst. As a result, 1,4-dihydropyrrolo[3,2-b]pyrroles were obtained in the highest yields reported to date. The scope and limitation studies showed that this new method was particularly efficient for sterically hindered aldehydes (yields 45-4996). Pentaaryl- and hexaaryl-1,4-dihydropyrrolo[3,2b]pyrroles were prepared from tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrroles via direct arylation by employing both electron-poor and electron-rich aromatic and heteroaromatic haloarenes. Strategic placement of electron-withdrawing substituents at the 2-, 3-, 5-, and 6-positions produced an acceptor donor acceptor type fluorophore. The resulting multiply substituted heteropentalenes displayed intriguing optical properties. The relationship between the structure and photophysical properties for all compounds were directly compared and thoroughly elucidated. All synthesized products displayed strong blue fluorescence and exhibited moderate to large Stokes shifts (3000-7300 cm(-1)) as well as high quantum yields of fluorescence up to 88%. Two-photon absorption cross-section values measured in the near-IR region were surprisingly high (hundreds of GM), given the limited conjugation in these propeller-shaped dyes.
OriginalsprogEngelsk
TidsskriftJournal of Organic Chemistry
Vol/bind79
Udgave nummer7
Sider (fra-til)3119-3128
ISSN0022-3263
DOI
StatusUdgivet - 2014

Emneord

  • CATALYZED DIRECT ARYLATION ORGANIC THERMAL-REACTIONS LIGHT-EMITTING-DIODES H BOND ACTIVATION 2-PHOTON ABSORPTION PYRROLE DERIVATIVES PALLADIUM DYES AZIDOACRYLATES HETEROACENES

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title = "Tetraaryl-, Pentaaryl-, and Hexaaryl-1,4-dihydropyrrolo 3,2-b pyrroles: Synthesis and Optical Properties",
abstract = "Efficient conditions for the synthesis of tetra-, penta-, and hexasubstituted derivatives of 1,4-dihydropyrrolo[3,2-b]pyrrole were developed. The tetraaryl derivatives were obtained in a novel one-pot reaction among aromatic aldehydes, aromatic amines, and butane-2,3-dione. After a thorough examination of various reaction parameters (solvent, acid, temperature) p-toluenesulfonic acid was identified as the crucial catalyst. As a result, 1,4-dihydropyrrolo[3,2-b]pyrroles were obtained in the highest yields reported to date. The scope and limitation studies showed that this new method was particularly efficient for sterically hindered aldehydes (yields 45-4996). Pentaaryl- and hexaaryl-1,4-dihydropyrrolo[3,2b]pyrroles were prepared from tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrroles via direct arylation by employing both electron-poor and electron-rich aromatic and heteroaromatic haloarenes. Strategic placement of electron-withdrawing substituents at the 2-, 3-, 5-, and 6-positions produced an acceptor donor acceptor type fluorophore. The resulting multiply substituted heteropentalenes displayed intriguing optical properties. The relationship between the structure and photophysical properties for all compounds were directly compared and thoroughly elucidated. All synthesized products displayed strong blue fluorescence and exhibited moderate to large Stokes shifts (3000-7300 cm(-1)) as well as high quantum yields of fluorescence up to 88{\%}. Two-photon absorption cross-section values measured in the near-IR region were surprisingly high (hundreds of GM), given the limited conjugation in these propeller-shaped dyes.",
keywords = "CATALYZED DIRECT ARYLATION ORGANIC THERMAL-REACTIONS LIGHT-EMITTING-DIODES H BOND ACTIVATION 2-PHOTON ABSORPTION PYRROLE DERIVATIVES PALLADIUM DYES AZIDOACRYLATES HETEROACENES",
author = "M. Krzeszewski and B. Thorsted and J. Brewer and Gryko, {D. T.}",
note = "ISI Document Delivery No.: AE5GT Times Cited: 3 Cited Reference Count: 61 Krzeszewski, Maciej Thorsted, Bjarne Brewer, Jonathan Gryko, Daniel T. Gryko, Daniel/A-7998-2008; Brewer, Jonathan/C-7079-2012; Thorsted, Bjarne/B-2588-2014 Brewer, Jonathan/0000-0002-3444-1715; Thorsted, Bjarne/0000-0001-9743-1699 Foundation for Polish Science (Mistrz programme); European Community's Seventh Framework Programme under the TOPBIO project [264362]; Danish Molecular Biomedical Imaging Center (DaMBIC); Carlsberg Foundation Financial support of our work from the Foundation for Polish Science (Mistrz programme) is gratefully acknowledged. The research leading to these results has received partial funding from the European Community's Seventh Framework Programme under the TOPBIO project, grant agreement no. 264362. J.B. gratefully acknowledges support from the Danish Molecular Biomedical Imaging Center (DaMBIC) and the Carlsberg Foundation. We thank Anita Janiga and Yevgen Poronik for useful suggestions and Jillian Larsen (UC Riverside) for amending the manuscript. 3 AMER CHEMICAL SOC WASHINGTON J ORG CHEM",
year = "2014",
doi = "10.1021/jo5002643",
language = "English",
volume = "79",
pages = "3119--3128",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "7",

}

Tetraaryl-, Pentaaryl-, and Hexaaryl-1,4-dihydropyrrolo 3,2-b pyrroles: Synthesis and Optical Properties. / Krzeszewski, M.; Thorsted, B.; Brewer, J.; Gryko, D. T.

I: Journal of Organic Chemistry, Bind 79, Nr. 7, 2014, s. 3119-3128.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Tetraaryl-, Pentaaryl-, and Hexaaryl-1,4-dihydropyrrolo 3,2-b pyrroles: Synthesis and Optical Properties

AU - Krzeszewski, M.

AU - Thorsted, B.

AU - Brewer, J.

AU - Gryko, D. T.

N1 - ISI Document Delivery No.: AE5GT Times Cited: 3 Cited Reference Count: 61 Krzeszewski, Maciej Thorsted, Bjarne Brewer, Jonathan Gryko, Daniel T. Gryko, Daniel/A-7998-2008; Brewer, Jonathan/C-7079-2012; Thorsted, Bjarne/B-2588-2014 Brewer, Jonathan/0000-0002-3444-1715; Thorsted, Bjarne/0000-0001-9743-1699 Foundation for Polish Science (Mistrz programme); European Community's Seventh Framework Programme under the TOPBIO project [264362]; Danish Molecular Biomedical Imaging Center (DaMBIC); Carlsberg Foundation Financial support of our work from the Foundation for Polish Science (Mistrz programme) is gratefully acknowledged. The research leading to these results has received partial funding from the European Community's Seventh Framework Programme under the TOPBIO project, grant agreement no. 264362. J.B. gratefully acknowledges support from the Danish Molecular Biomedical Imaging Center (DaMBIC) and the Carlsberg Foundation. We thank Anita Janiga and Yevgen Poronik for useful suggestions and Jillian Larsen (UC Riverside) for amending the manuscript. 3 AMER CHEMICAL SOC WASHINGTON J ORG CHEM

PY - 2014

Y1 - 2014

N2 - Efficient conditions for the synthesis of tetra-, penta-, and hexasubstituted derivatives of 1,4-dihydropyrrolo[3,2-b]pyrrole were developed. The tetraaryl derivatives were obtained in a novel one-pot reaction among aromatic aldehydes, aromatic amines, and butane-2,3-dione. After a thorough examination of various reaction parameters (solvent, acid, temperature) p-toluenesulfonic acid was identified as the crucial catalyst. As a result, 1,4-dihydropyrrolo[3,2-b]pyrroles were obtained in the highest yields reported to date. The scope and limitation studies showed that this new method was particularly efficient for sterically hindered aldehydes (yields 45-4996). Pentaaryl- and hexaaryl-1,4-dihydropyrrolo[3,2b]pyrroles were prepared from tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrroles via direct arylation by employing both electron-poor and electron-rich aromatic and heteroaromatic haloarenes. Strategic placement of electron-withdrawing substituents at the 2-, 3-, 5-, and 6-positions produced an acceptor donor acceptor type fluorophore. The resulting multiply substituted heteropentalenes displayed intriguing optical properties. The relationship between the structure and photophysical properties for all compounds were directly compared and thoroughly elucidated. All synthesized products displayed strong blue fluorescence and exhibited moderate to large Stokes shifts (3000-7300 cm(-1)) as well as high quantum yields of fluorescence up to 88%. Two-photon absorption cross-section values measured in the near-IR region were surprisingly high (hundreds of GM), given the limited conjugation in these propeller-shaped dyes.

AB - Efficient conditions for the synthesis of tetra-, penta-, and hexasubstituted derivatives of 1,4-dihydropyrrolo[3,2-b]pyrrole were developed. The tetraaryl derivatives were obtained in a novel one-pot reaction among aromatic aldehydes, aromatic amines, and butane-2,3-dione. After a thorough examination of various reaction parameters (solvent, acid, temperature) p-toluenesulfonic acid was identified as the crucial catalyst. As a result, 1,4-dihydropyrrolo[3,2-b]pyrroles were obtained in the highest yields reported to date. The scope and limitation studies showed that this new method was particularly efficient for sterically hindered aldehydes (yields 45-4996). Pentaaryl- and hexaaryl-1,4-dihydropyrrolo[3,2b]pyrroles were prepared from tetraaryl-1,4-dihydropyrrolo[3,2-b]pyrroles via direct arylation by employing both electron-poor and electron-rich aromatic and heteroaromatic haloarenes. Strategic placement of electron-withdrawing substituents at the 2-, 3-, 5-, and 6-positions produced an acceptor donor acceptor type fluorophore. The resulting multiply substituted heteropentalenes displayed intriguing optical properties. The relationship between the structure and photophysical properties for all compounds were directly compared and thoroughly elucidated. All synthesized products displayed strong blue fluorescence and exhibited moderate to large Stokes shifts (3000-7300 cm(-1)) as well as high quantum yields of fluorescence up to 88%. Two-photon absorption cross-section values measured in the near-IR region were surprisingly high (hundreds of GM), given the limited conjugation in these propeller-shaped dyes.

KW - CATALYZED DIRECT ARYLATION ORGANIC THERMAL-REACTIONS LIGHT-EMITTING-DIODES H BOND ACTIVATION 2-PHOTON ABSORPTION PYRROLE DERIVATIVES PALLADIUM DYES AZIDOACRYLATES HETEROACENES

U2 - 10.1021/jo5002643

DO - 10.1021/jo5002643

M3 - Journal article

VL - 79

SP - 3119

EP - 3128

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 7

ER -