Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes

Julius Knöller; Guoyun Meng; Xiang Wang; David Hall; Anton Pershin; David Beljonne; Yoann Olivier; Sabine Laschat; Eli Zysman-Colman; Suning Wang

doi:10.1002/anie.201912340

Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes

Julius Knöller, Guoyun Meng, Xiang Wang, David Hall, Anton Pershin, David Beljonne, Yoann Olivier, Sabine Laschat, Eli Zysman-Colman, Suning Wang

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

Abstract

New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3 - 6a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)₃ in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N- anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo substituted B,N,B-benzo[4]helicenes 2a/2b via intramolecular borylation and sequential B-Mes bond cleavage in presence of BBr3. Subsequent reaction of 2a/2b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ∆E_ST suggest the potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

Original language	English
Journal	Angewandte Chemie International Edition
Volume	Early View
Early online date	16 Jan 2020
DOIs	https://doi.org/10.1002/anie.201912340
Publication status	E-pub ahead of print - 16 Jan 2020

Keywords

Synthetic methods
Boron
Luminescence
B,N,B- benzo[4]helicenes
Divergent synthesis

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10.1002/anie.201912340

Knoeller_et_al-2019-Angewandte_Chemie_International_Edition[1]
Copyright © 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/anie.201912340
Accepted author manuscript, 2.4 MB

Blue-Emitting TADF Materials: Blue-Emitting TADF Materials for OLEDs Based on a Lewis Acid-Containing Acceptor
Zysman-Colman, E. (PI)
The Leverhulme Trust
1/08/16 → 30/04/22
Project: Standard

Intramolecular Borylation via Sequential B-Mes Bond Cleavage for the Divergent Synthesis of B,N,B-doped Benzo[4]helicenes (dataset)
Knöller, J. A. (Creator), Meng, G. (Creator), Wang, X. (Creator), Hall, D. (Creator), Pershin, A. (Creator), Beljonne, D. (Creator), Olivier, Y. (Creator), Laschat, S. (Creator), Zysman-Colman, E. (Creator) & Wang, S. (Creator), University of St Andrews, 28 Jan 2020
DOI: 10.17630/55e305b2-410e-44d3-9300-96123c69fe8d
Dataset

File

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Knöller, J., Meng, G., Wang, X., Hall, D., Pershin, A., Beljonne, D., Olivier, Y., Laschat, S., Zysman-Colman, E., & Wang, S. (2020). Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes. Angewandte Chemie International Edition, Early View. Advance online publication. https://doi.org/10.1002/anie.201912340

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title = "Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes",

abstract = "New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3 - 6a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)3 in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N- anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo substituted B,N,B-benzo[4]helicenes 2a/2b via intramolecular borylation and sequential B-Mes bond cleavage in presence of BBr3. Subsequent reaction of 2a/2b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ∆EST suggest the potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).",

keywords = "Synthetic methods, Boron, Luminescence, B,N,B- benzo[4]helicenes, Divergent synthesis",

author = "Julius Kn{\"o}ller and Guoyun Meng and Xiang Wang and David Hall and Anton Pershin and David Beljonne and Yoann Olivier and Sabine Laschat and Eli Zysman-Colman and Suning Wang",

note = "Authors thank the Natural Sciences and Engineering Research Council of Canada and the Leverhulme Trust (RPG-2016-47) for financial support. J. A. Kn{\"o}ller thanks the Baden W{\"u}rttemberg Stiftung for a scholarship as well as Queen's and Stuttgart University for enabling this research through the Dual Degree Masters program.",

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doi = "10.1002/anie.201912340",

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T1 - Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes

AU - Knöller, Julius

AU - Meng, Guoyun

AU - Wang, Xiang

AU - Hall, David

AU - Pershin, Anton

AU - Beljonne, David

AU - Olivier, Yoann

AU - Laschat, Sabine

AU - Zysman-Colman, Eli

AU - Wang, Suning

N1 - Authors thank the Natural Sciences and Engineering Research Council of Canada and the Leverhulme Trust (RPG-2016-47) for financial support. J. A. Knöller thanks the Baden Württemberg Stiftung for a scholarship as well as Queen's and Stuttgart University for enabling this research through the Dual Degree Masters program.

PY - 2020/1/16

Y1 - 2020/1/16

N2 - New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3 - 6a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)3 in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N- anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo substituted B,N,B-benzo[4]helicenes 2a/2b via intramolecular borylation and sequential B-Mes bond cleavage in presence of BBr3. Subsequent reaction of 2a/2b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ∆EST suggest the potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

AB - New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3 - 6a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)3 in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N- anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo substituted B,N,B-benzo[4]helicenes 2a/2b via intramolecular borylation and sequential B-Mes bond cleavage in presence of BBr3. Subsequent reaction of 2a/2b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ∆EST suggest the potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

KW - Synthetic methods

KW - Boron

KW - Luminescence

KW - B,N,B- benzo[4]helicenes

KW - Divergent synthesis

U2 - 10.1002/anie.201912340

DO - 10.1002/anie.201912340

M3 - Article

SN - 1433-7851

VL - Early View

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

ER -

Intramolecular borylation via sequential B-Mes bond cleavage for the divergent synthesis of B,N,B-doped benzo[4]helicenes

Abstract

Keywords

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Projects

Blue-Emitting TADF Materials: Blue-Emitting TADF Materials for OLEDs Based on a Lewis Acid-Containing Acceptor

Datasets

Intramolecular Borylation via Sequential B-Mes Bond Cleavage for the Divergent Synthesis of B,N,B-doped Benzo[4]helicenes (dataset)

Cite this