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Lanthanide-catalyzed cyclocarbonylation and cyclothiocarbonylation: a facile synthesis of benzannulated 1,3-diheteroatom five- and six-membered heterocycles

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Abstract

La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol, o-aminothiophenol, catechols and anilines ortho-substituted by CH2NH2 and CONH2 to form, respectively, the corresponding benzimidazolones, benzoxazolones, benzothiazolones, benzodioxolones, 3,4-dihydroquinazolin-2(1H)-one, and quinazolinediones. These results represent the first example of lanthanide-catalyzed carbonylation. This methodology is also applicable for the preparation of various benzannulated 1,3-diheteroatom cyclic thioketones starting from aryl/alkyl isothiocyanates or CS2 in good to excellent yields. Based on the results of experiments performed using an o-aminobenzamido dianion lanthanide complex, a general mechanism, involving the tandem reaction of two lanthanide-ligand bonds with one heterocumulene molecule, is proposed as well.

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Authors and Affiliations

  1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai, 200433, China

    YuFeng Jing, RuiTing Liu, YangHui Lin & XiGeng Zhou

  2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032, China

    XiGeng Zhou

Authors
  1. YuFeng Jing
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  2. RuiTing Liu
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  3. YangHui Lin
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Correspondence to YangHui Lin or XiGeng Zhou.

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Dedicated to Professor Qian Changtao on the occasion of his 80th birthday.

LIN YangHui obtained his BSc and MS degrees from East China Normal University in 1990 and 1995, respectively. Subsequently, He joined the faculty of Old Shanghai Medical University. He received a PhD from Fudan University in 2000. Now he is the faculty of Fudan University as a full assistant professor of chemistry. His research interests include inorganic material and metalorganic chemistry.

ZHOU XiGeng received his BSc from Central China Normal University in 1986, MSc from Anhui Normal University in 1989 and PhD from Nanjing University in 1996 under the supervision of Prof. Xiaozeng You. He joined the Department of Chemistry at Fudan University in 1996, and was promoted to professor in 2000. His research interests include organometallic chemistry with a focus on synthesis, structure and reactivity of new organolanthanide complexes, and more recently, new methodology for synthesis of organic compounds.

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Jing, Y., Liu, R., Lin, Y. et al. Lanthanide-catalyzed cyclocarbonylation and cyclothiocarbonylation: a facile synthesis of benzannulated 1,3-diheteroatom five- and six-membered heterocycles. Sci. China Chem. 57, 1117–1125 (2014). https://doi.org/10.1007/s11426-014-5149-0

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  • DOI: https://doi.org/10.1007/s11426-014-5149-0

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