Intramolecular Borylation via Sequential B−Mes Bond Cleavage for the Divergent Synthesis of B,N,B-Doped Benzo[4]helicenes

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

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Abstract

New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3–6 a/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 2 a/2 b via intramolecular borylation and sequential B−Mes bond cleavage in the presence of BBr₃. Subsequent reaction of 2 a/2 b 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 ΔE_ST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

Original language	English
Pages (from-to)	3156-3160
Number of pages	5
Journal	Angewandte Chemie. International edition
Volume	59
Issue number	8
DOIs	https://doi.org/10.1002/anie.201912340
Publication status	Published - 17 Feb 2020

Keywords

B,N,B-benzo[4]helicenes
boron
divergent synthesis
luminescence
synthetic methods

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10.1002/anie.201912340

2020_OlivierY_articleAccepted author manuscript, 520 KB

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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 3–6 a/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 2 a/2 b via intramolecular borylation and sequential B−Mes bond cleavage in the presence of BBr3. Subsequent reaction of 2 a/2 b 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 ΔEST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).",

keywords = "B,N,B-benzo[4]helicenes, boron, divergent synthesis, luminescence, synthetic methods",

author = "Kn{\"o}ller, {Julius A.} 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 = "Funding Information: We 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. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = feb,

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doi = "10.1002/anie.201912340",

language = "English",

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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 A.

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 - Funding Information: We 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. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/2/17

Y1 - 2020/2/17

N2 - New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3–6 a/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 2 a/2 b via intramolecular borylation and sequential B−Mes bond cleavage in the presence of BBr3. Subsequent reaction of 2 a/2 b 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 ΔEST suggest their 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 3–6 a/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 2 a/2 b via intramolecular borylation and sequential B−Mes bond cleavage in the presence of BBr3. Subsequent reaction of 2 a/2 b 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 ΔEST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).

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

KW - boron

KW - divergent synthesis

KW - luminescence

KW - synthetic methods

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IS - 8

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Intramolecular Borylation via Sequential B−Mes Bond Cleavage for the Divergent Synthesis of B,N,B-Doped Benzo[4]helicenes

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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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CCDC 1946485: Experimental Crystal Structure Determination

CCDC 1946489: Experimental Crystal Structure Determination

CCDC 1946487: Experimental Crystal Structure Determination

Cite this