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Regioselective "hydroamination" of alk-3-ynones with non-symmetrical o-phenylenediamines. Synthesis of diversely substituted 3H-1,5-benzodiazepines via (Z)-3-amino-2-alkenones

Young, Jonathon; Schafer, Christian; Solan, Agnes; Baldrica, Anthony; Belcher, Miranda; Nisanci, Bilal; Wheeler, Kraig A.; Trivedi, Evan R.; Torok, Bela; Dembinski, Roman


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        "affiliation": "Oakland Univ, Dept Chem, 146 Lib Dr, Rochester, MI 48309 USA", 
        "name": "Young, Jonathon"
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      {
        "affiliation": "Univ Massachusetts, Dept Chem, 100 Morrissey Blvd, Boston, MA 02125 USA", 
        "name": "Schafer, Christian"
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      {
        "affiliation": "Oakland Univ, Dept Chem, 146 Lib Dr, Rochester, MI 48309 USA", 
        "name": "Solan, Agnes"
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      {
        "affiliation": "Oakland Univ, Dept Chem, 146 Lib Dr, Rochester, MI 48309 USA", 
        "name": "Baldrica, Anthony"
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      {
        "affiliation": "Oakland Univ, Dept Chem, 146 Lib Dr, Rochester, MI 48309 USA", 
        "name": "Belcher, Miranda"
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      {
        "name": "Nisanci, Bilal"
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      {
        "affiliation": "Eastern Illinois Univ, Dept Chem, 600 Lincoln Ave, Charleston, IL 61920 USA", 
        "name": "Wheeler, Kraig A."
      }, 
      {
        "affiliation": "Oakland Univ, Dept Chem, 146 Lib Dr, Rochester, MI 48309 USA", 
        "name": "Trivedi, Evan R."
      }, 
      {
        "affiliation": "Univ Massachusetts, Dept Chem, 100 Morrissey Blvd, Boston, MA 02125 USA", 
        "name": "Torok, Bela"
      }, 
      {
        "name": "Dembinski, Roman"
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    "description": "The reaction of alk-3-yn-1-ones (a bifunctional reagent) with o-phenylenediamines provides an effective synthetic method with high atom economy for the preparation of diversely substituted 1,5-3H-benzodiazepines. The reaction initially leads to the formation of conjugated enaminones (3-amino-2alkenones, 51-99%), at room temperature, which constitutes a formal non-catalyzed hydroamination of the non-conjugated alkyne. Non-symmetrical o-phenylenediamines react in a regioselective fashion with respect to amino groups. Both the direct microwave-accelerated reaction of o-phenylenediamines with alkynones in ethanol and the intramolecular cyclization of intermediate enaminones in ethanol/acetic acid lead to substituted 1,5-benzodiazepines with good yields (39-92 and 26-99%). The regio-and stereochemical outcomes of these processes are confirmed by the X-ray structure determination of (Z)-3-[(2-amino-4-methylanilino)-4-(4-methylphenyl)-1-phenylbut-2-en-1-one],4-[(4-methylphenyl) methyl]-7-nitro-2-phenyl-3H-1,5-benzodiazepine and 6,8-dimethyl-4-(4-methylbenzyl)-2-phenyl-3Hbenzo[b][1,5]diazepine.", 
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      "pages": "107081-107093", 
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    "title": "Regioselective \"hydroamination\" of alk-3-ynones with non-symmetrical o-phenylenediamines. Synthesis of diversely substituted 3H-1,5-benzodiazepines via (Z)-3-amino-2-alkenones"
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