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Red-Hair-Inspired Chromogenic System Based on a Proton-Switched Dehydrogenative Free-Radical Coupling
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    Red-Hair-Inspired Chromogenic System Based on a Proton-Switched Dehydrogenative Free-Radical Coupling
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    Department of Chemical Sciences, University of Naples “Federico II”, Via Cinthia 4, I-80126 Naples, Italy, Department of Chemistry “Ciamician”, University of Bologna, Via S. Giacomo 11, I-40126 Bologna, Italy, and Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126 Pisa, Italy
    †University of Naples “Federico II”.
    ‡University of Bologna.
    §Scuola Normale Superiore.
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    Organic Letters

    Cite this: Org. Lett. 2013, 15, 19, 4944–4947
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    https://doi.org/10.1021/ol402161j
    Published September 17, 2013
    Copyright © 2013 American Chemical Society

    Abstract

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    In the presence of micromolar peroxides or biometals (Fe(III), Cu(II), V(V) salts), and following a strong acid input, the stable 3-phenyl-2H-1,4-benzothiazine is efficiently converted to a green-blue Δ2,2′-bi(2H-1,4-benzothiazine) chromophore via dehydrogenative coupling of a 1,4-benzothiazinyl radical. The new system is of potential practical interest for colorimetric peroxide and redox biometal detection.

    Copyright © 2013 American Chemical Society

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    Supporting Information

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    Experimental procedures, spectral and computational data for 13, complete computational and EPR data for 3-phenyl-1,4-benzothiazinyl radical. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

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    This article is cited by 13 publications.

    1. Luca Valgimigli, Maria Laura Alfieri, Riccardo Amorati, Andrea Baschieri, Orlando Crescenzi, Alessandra Napolitano, Marco d’Ischia. Proton-Sensitive Free-Radical Dimer Evolution Is a Critical Control Point for the Synthesis of Δ2,2′-Bibenzothiazines. The Journal of Organic Chemistry 2020, 85 (17) , 11440-11448. https://doi.org/10.1021/acs.joc.0c01520
    2. Xianqiang Huang, Nianxin Rong, Pengfei Li, Guodong Shen, Qiang Li, Nana Xin, Chuansheng Cui, Jichui Cui, Bingchuan Yang, Dacheng Li, Changqiu Zhao, Jianmin Dou, Bo Wang. AIBN-Promoted Synthesis of Bibenzo[b][1,4]thiazines by the Condensation of 2,2′-Dithiodianiline with Methyl Aryl Ketones. Organic Letters 2018, 20 (11) , 3332-3336. https://doi.org/10.1021/acs.orglett.8b01238
    3. Ya-mei Lin, Guo-ping Lu, Rong-kang Wang, and Wen-bin Yi . Radical Route to 1,4-Benzothiazine Derivatives from 2-Aminobenzenethiols and Ketones under Transition-Metal-Free Conditions. Organic Letters 2016, 18 (24) , 6424-6427. https://doi.org/10.1021/acs.orglett.6b03324
    4. Maria Laura Alfieri, Lucia Panzella. The Multifaceted Opportunities Provided by the Pheomelanin-Inspired 1,4-Benzothiazine Chromophore: A Still-Undervalued Issue. Molecules 2023, 28 (17) , 6237. https://doi.org/10.3390/molecules28176237
    5. Péter Kisszékelyi, Tibor Peňaška, Klára Stankovianska, Mária Mečiarová, Radovan Šebesta. Derivatives of benzo-1,4-thiazine-3-carboxylic acid and the corresponding amino acid conjugates. Beilstein Journal of Organic Chemistry 2022, 18 , 1195-1202. https://doi.org/10.3762/bjoc.18.124
    6. Maria Laura Alfieri, Lucia Panzella, Orlando Crescenzi, Marco d’Ischia, Alessandra Napolitano. A cyanine-type homolog of the red hair bibenzothiazine chromophore combining reversible proton-sensing with a hydrophobic-to-hydrophilic switching response. Dyes and Pigments 2022, 197 , 109872. https://doi.org/10.1016/j.dyepig.2021.109872
    7. Yuquan Qi, Xiaoyu Gu, Xianqiang Huang, Guodong Shen, Bingchuan Yang, Qingpeng He, Zechun Xue, Mengcheng Du, Lilong Shi, Bing Yu. Microwave-assisted controllable synthesis of 2-acylbenzothiazoles and bibenzo[b][1,4]thiazines from aryl methyl ketones and disulfanediyldianilines. Chinese Chemical Letters 2021, 32 (11) , 3544-3547. https://doi.org/10.1016/j.cclet.2021.05.069
    8. Maria Laura Alfieri, Lucia Panzella, Orlando Crescenzi, Alessandra Napolitano, Marco d'Ischia. Nature‐Inspired Functional Chromophores from Biomimetic o ‐Quinone Chemistry. European Journal of Organic Chemistry 2021, 2021 (21) , 2982-2989. https://doi.org/10.1002/ejoc.202100341
    9. Maria Laura Alfieri, Lucia Panzella, Marco d’Ischia, Alessandra Napolitano. Bioinspired Heterocyclic Partnership in a Cyanine-Type Acidichromic Chromophore. Molecules 2020, 25 (17) , 3817. https://doi.org/10.3390/molecules25173817
    10. Mandapati Bhargava Reddy, Ramasamy Anandhan. Visible light initiated amino group ortho -directed copper( i )-catalysed aerobic oxidative C(sp)–S coupling reaction: synthesis of substituted 2-phenylbenzothiazoles via thia-Wolff rearrangement. Chemical Communications 2020, 56 (26) , 3781-3784. https://doi.org/10.1039/D0CC00815J
    11. Kazuhiro Kobayashi, Hiroki Inouchi, Ryo Hasegawa, Kazuki Kawano. Synthesis of 3-(Alkylsulfanyl)-1,4-benzothiazine Derivatives Based on Cyclization of 2-[(Cyanomethyl)sulfanyl]phenyl Isothiocyanate. HETEROCYCLES 2017, 94 (12) , 2307. https://doi.org/10.3987/COM-17-13823
    12. Loredana Leone, Alessandro Pezzella, Orlando Crescenzi, Alessandra Napolitano, Vincenzo Barone, Marco d'Ischia. Trichocyanines: a Red-Hair-Inspired Modular Platform for Dye-Based One-Time-Pad Molecular Cryptography. ChemistryOpen 2015, 4 (3) , 370-377. https://doi.org/10.1002/open.201402164
    13. Alessandra Napolitano, Lucia Panzella, Giuseppe Monfrecola, Marco d'Ischia. Pheomelanin-induced oxidative stress: bright and dark chemistry bridging red hair phenotype and melanoma. Pigment Cell & Melanoma Research 2014, 27 (5) , 721-733. https://doi.org/10.1111/pcmr.12262

    Organic Letters

    Cite this: Org. Lett. 2013, 15, 19, 4944–4947
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ol402161j
    Published September 17, 2013
    Copyright © 2013 American Chemical Society

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