<i>tert</i>-Amino Effect-Promoted Rearrangement of Aryl Isothiocyanate: A Versatile Approach to Benzimidazothiazepines and Benzimidazothioethers

Geng, Xinyu; Liu, Siyuan; Wang, Wenyao; Qü, Jingping; Wang, Baomin

doi:10.1021/acs.joc.0c01806

Cited by 10 publications

(3 citation statements)

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“…Pyrrolo[1,2- a ]benzimidazole was reported from an o -lactam substituted aniline cyclization using di- t -butyl sulfoxide/NBS via an aza-Wittig type-reaction ( Scheme 21 b) [ 76 ]. 1-(2-Isothiocyanatophenyl)pyrrolidines cyclize under thermal acidic conditions to benzimidazothiazepines ( Scheme 21 c) [ 77 ].…”

Section: Syntheses Of Ring-fused Benzimidazoles and Imidazobenzimidazolesmentioning

confidence: 99%

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Advances in the Synthesis of Ring-Fused Benzimidazoles and Imidazobenzimidazoles

et al. 2021

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This review article provides a perspective on the synthesis of alicyclic and heterocyclic ring-fused benzimidazoles, imidazo[4,5-f]benzimidazoles, and imidazo[5,4-f]benzimidazoles. These heterocycles have a plethora of biological activities with the iminoquinone and quinone derivatives displaying potent bioreductive antitumor activity. Synthesis is categorized according to the cyclization reaction and mechanisms are detailed. Nitrobenzene reduction, cyclization of aryl amidines, lactams and isothiocyanates are described. Protocols include condensation, cross-dehydrogenative coupling with transition metal catalysis, annulation onto benzimidazole, often using CuI-catalysis, and radical cyclization with homolytic aromatic substitution. Many oxidative transformations are under metal-free conditions, including using thermal, photochemical, and electrochemical methods. Syntheses of diazole analogues of mitomycin C derivatives are described. Traditional oxidations of o-(cycloamino)anilines using peroxides in acid via the t-amino effect remain popular.

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Section: Syntheses Of Ring-fused Benzimidazoles and Imidazobenzimidazolesmentioning

confidence: 99%

“… Synthesis from ( a ) o -haloarylamidine [ 75 ], ( b ) a lactam derivative of o -phenyldiamine [ 76 ], and ( c ) a rearrangement of aryl isothiocyanates [ 77 ]. …”

Section: Figures and Schemesmentioning

confidence: 99%

Advances in the Synthesis of Ring-Fused Benzimidazoles and Imidazobenzimidazoles

et al. 2021

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“…Furthermore, the spatial arrangement of the atoms and the conformation of the seven-membered ring, which was obtained by X-ray diffraction analysis [8] or theoretical methods [12], is of great importance for amine-imine tautomeric chemistry. But only a few compounds that include the 1,3-thiazepine ring containing (with Refcodes in CCDC [13]: BEVNEW [14], BEVNIA [14], JEPYOS [15], QIBMET [16], QIBMET01, QIBMET02, QIBMET03, QIBMET04 [17], QOZMUO [18], RENVOV [8], RENVIP [8], and YUKPIE [19]) were characterized by the single-crystal XRD method. All of these deposited structures belong to an imine form.…”

Section: Introductionmentioning

confidence: 99%

Molecular and crystal structure characteristics of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride and 2-phenyliminohexahydro-1,3-thiazepine

et al. 2023

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The current research includes the synthesis and crystallographic characterization of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride (HPAT) and 2-phenyliminohexa- hydro-1,3-thiazepine (PIT) compounds. 2-Phenylaminotetrahydro-1,3-thiazepine hydro-chloride was synthesized by cyclization of 1-(4-hydroxybutyl)-3-phenylthiourea in an acidic condition. The second compound, 2-phenyliminohexahydro-1,3-thiazepine, was obtained by neutralizing 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride with sodium hydrocarbonate. Both compounds were characterized by the single-crystal X-ray diffraction method. Crystal data for C11H17N2OClS (HPAT): orthorhombic, space group P212121 (no. 19), a = 4.97183(14) Å, b = 15.1169(4) Å, c = 17.7376(5) Å, V = 1333.14(6) Å3, Z = 4, μ(CuKα) = 3.859 mm-1, Dcalc = 1.299 g/cm3, 9243 reflections measured (7.684° ≤ 2Θ ≤ 152.042°), 2749 unique (Rint = 0.0314, Rsigma = 0.0255) which were used in all calculations. The final R1 was 0.0351 (I > 2σ(I)) and wR2 was 0.0911 (all data). Crystal data for C11H14N2S (PIT): monoclinic, space group P21/n (no. 14), a = 9.6303(9) Å, b = 9.8938(6) Å, c = 11.5627(9) Å, β = 103.419(8)°, V = 1071.62(14) Å3, Z = 4, μ(CuKα) = 2.357 mm-1, Dcalc = 1.279 g/cm3, 3938 reflections measured (10.798° ≤ 2Θ ≤ 152.328°), 2172 unique (Rint = 0.0288, Rsigma = 0.0330) that were used in all calculations. The final R1 was 0.0431 (I > 2σ(I)) and wR2 was 0.1219 (all data). The asymmetric unit of HPAT contains one protonated amine, one chlorine anion, and one water molecule. Chlorine anion and water molecules play the role of the bridge in chain formation along the a- and b-axis through H-bonds with N-H hydrogen atoms. Furthermore, the Hirshfeld surface analyses are performed to determine the nature of the intermolecular contacts stabilizing the crystal structures of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride and 2-phenyliminohexahydro-1,3-thiazepine.

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Pd‐Catalyzed MIA‐Directed Acetoxylation of Benzylamines and Computational Study

et al. 2022

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The direct acetoxylation of substituted benzylamines has been accomplished through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. A diverse array of phenylalanine substrates is amenable to this protocol, providing acetoxylation benzylamine derivatives with good to high efficiency. Computational results revealed that HOAc enhanced the stability of Pd−O bond, which obviously accelerate the reductive elimination step of the acetoxylation process.

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tert-Amino Effect-Promoted Rearrangement of Aryl Isothiocyanate: A Versatile Approach to Benzimidazothiazepines and Benzimidazothioethers

Cited by 10 publications

References 60 publications

Advances in the Synthesis of Ring-Fused Benzimidazoles and Imidazobenzimidazoles

Advances in the Synthesis of Ring-Fused Benzimidazoles and Imidazobenzimidazoles

Molecular and crystal structure characteristics of 2-phenylaminotetrahydro-1,3-thiazepine hydrochloride and 2-phenyliminohexahydro-1,3-thiazepine

Pd‐Catalyzed MIA‐Directed Acetoxylation of Benzylamines and Computational Study

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