Brønsted Acid Catalyzed Cyclization of Inert N-Substituted Pyrroles to Benzo[f]pyrrolo[1,2-a][1,4]diazepines

Zeng Gao; Jinlong Qian; Huameng Yang; Jinlong Zhang; Gaoxi Jiang

doi:10.1055/a-1468-5725

Synlett, Table of Contents

Synlett 2021; 32(09): 930-934
DOI: 10.1055/a-1468-5725

letter

Brønsted Acid Catalyzed Cyclization of Inert N-Substituted Pyrroles to Benzo[f]pyrrolo[1,2-a][1,4]diazepines

Zeng Gao

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Jinlong Qian

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

,

Huameng Yang

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

,

Jinlong Zhang∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

,

Gaoxi Jiang∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

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Abstract

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Abstract

Two approaches involving intramolecular and intermolecular cyclization, respectively, have been developed for the direct and practical construction of a series of important benzo[f]pyrrolo[1,2-a][1,4]azepines by using Brønsted acid catalysts. Upon catalysis by TsOH, the intramolecular dehydroxylation/ring closure of 3-hydroxy-2-[2-(1H-pyrrol-1-yl)benzyl]isoindolin-1-ones provided various racemic benzo[f]pyrrolo[1,2-a][1,4]azepines in high yields. Furthermore, enantioenriched benzo[f]pyrrolo[1,2-a][1,4]azepines were also obtained by chiral phosphoric acid catalyzed intermolecular addition of [2-(1H-pyrrol-1-yl)phenyl]methanamines to 2-formylbenzoates under mild conditions.

Key words

Brønsted acid catalysis - cyclization - pyrroles - intermolecular addition - azepines - asymmetric catalysis

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References

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12 9H-Isoindolo[1,2-c]pyrrolo[1,2-a][1,4]benzodiazepin-11(15bH)-ones 2a–q; General Procedure (Intramolecular Reaction) The appropriate isoindolone 1 (0.2 mmol, 1.0 equiv) and TsOH (1 mol%) were stirred in CH₂Cl₂ (1 mL) at r.t. When the reaction was complete, the solvent was removed and the crude mixture was purified by flash column chromatography (silica gel, hexane–EtOAc). 9H-Isoindolo[1,2-c]pyrrolo[1,2-a][1,4]benzodiazepin-11(15bH)-ones 2a, 2q–t; General Procedure (Intermolecular Reaction) The appropriate amine 3 (0.1 mmol, 1.0 equiv), methyl 2-formylbenzoate (4a, 0.15 mmol, 1.5 equiv), chiral phosphoric acid A5 (5.0 mol%), and 4 Å MS (100 mg) were stirred in toluene (1.0 mL) at r.t. under N₂. Upon completion of the reaction, the solvent was removed and the crude mixture was purified by flash column chromatography. 9H-Isoindolo[1,2-c]pyrrolo[1,2-a][1,4]benzodiazepin-11(15bH)-one (2a) White solid; yield: 53.2 mg (93%); mp 192-195 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.91 (d, J = 7.5 Hz, 1 H), 7.64–7.44 (m, 6 H), 7.35 (t, J = 7.4 Hz, 1 H), 7.10 (d, J = 2.9 Hz, 1 H), 6.26 (t, J = 3.3 Hz, 1 H), 5.94 (d, J = 3.5 Hz, 1 H), 5.40 (s, 1 H), 5.06 (d, J = 13.9 Hz, 1 H), 4.17 (d, J = 13.9 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 167.0, 141.7, 140.2, 133.6, 131.5, 131.2, 130.0, 128.9, 128.5, 127.3, 124.0, 123.6, 121.8, 109.5, 107.2, 56.4, 44.6. CCDC 1964245 contains the supplementary crystallographic data for compound 2a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.

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