(E)-1-acetyl-3-(4,4-dimethyl-3,5-dioxacycloheptylidene)-2,5-piperazinedione | 141509-44-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-1-acetyl-3-(4,4-dimethyl-3,5-dioxacycloheptylidene)-2,5-piperazinedione
• 英文别名: (3E)-1-acetyl-3-(2,2-dimethyl-1,3-dioxepan-5-ylidene)piperazine-2,5-dione
• CAS: 141509-44-6
• 化学式: C₁₃H₁₈N₂O₅
• 分子量: 282.296
• InChiKey: CAUIIPDSKGTDKB-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4,4-二甲基-3,5,8-三氧杂双环[5,1,0]辛烷 在 lithium aluminium tetrahydride 、 重铬酸吡啶 、 potassium tert-butylate 、 三氟乙酸吡啶 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 68.0h， 生成 (E)-1-acetyl-3-(4,4-dimethyl-3,5-dioxacycloheptylidene)-2,5-piperazinedione
  参考文献：
  名称：

  Comparative studies on the reactivity of 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione, 1-acetyl-3-hydroxy-3-vinyl-2,5-piperazinedione, and bicyclomycin. Examination of a key structural element necessary for bicyclomycin-mediated transformations

  摘要：

  Two select mimics, 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione (8) and 1-acetyl-3-hydroxy-3-vinyl-2, 5-piperazinedione (7) of the structurally novel antibiotic, bicyclomycin (1), have been prepared. Comparison of the chemical reactivity of 7 versus 1 both in the presence and absence of added nucleophiles at various "pH" values has provided important new information concerning the role of key structural elements present in bicyclomycin. The product profiles determined for 7 indicated that modification of the terminal double bond proceeded through an alpha,beta-unsaturated ring imine intermediate (i.e., 43). Correspondingly, activation of the exo-methylene group in bicyclomycin is believed to occur through initial hemiaminal bond scission to give a ring-opened alpha,beta-unsaturated carbonyl species (i.e., 2). Functionalization of the terminal double bond in 7 has been shown to proceed under milder conditions than that required for 1. These results demonstrated that incorporation of the exo-methylene group within the O(2)-C(3)-C(4)-C(5) bridge in 1 required that the terminal double bond activation pathway proceed by an alternative, energetically more-demanding pathway than that observed for 7. Ramifications of the decreased reactivity noted for 1 are to allow other functional groups (i.e., the C(1)-triol moiety) in the antibiotic to have important catalytic roles in the drug modification processes and to permit thiolate species (the proposed biological targets?) to effectively compete with other nucleophiles for 2.

  DOI：

  10.1021/jo00039a028

文献信息

• Comparative studies on the reactivity of 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione, 1-acetyl-3-hydroxy-3-vinyl-2,5-piperazinedione, and bicyclomycin. Examination of a key structural element necessary for bicyclomycin-mediated transformations
  作者：Yeong Soo Oh、Harold Kohn

  DOI：10.1021/jo00039a028

  日期：1992.6

  Two select mimics, 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione (8) and 1-acetyl-3-hydroxy-3-vinyl-2, 5-piperazinedione (7) of the structurally novel antibiotic, bicyclomycin (1), have been prepared. Comparison of the chemical reactivity of 7 versus 1 both in the presence and absence of added nucleophiles at various "pH" values has provided important new information concerning the role of key structural elements present in bicyclomycin. The product profiles determined for 7 indicated that modification of the terminal double bond proceeded through an alpha,beta-unsaturated ring imine intermediate (i.e., 43). Correspondingly, activation of the exo-methylene group in bicyclomycin is believed to occur through initial hemiaminal bond scission to give a ring-opened alpha,beta-unsaturated carbonyl species (i.e., 2). Functionalization of the terminal double bond in 7 has been shown to proceed under milder conditions than that required for 1. These results demonstrated that incorporation of the exo-methylene group within the O(2)-C(3)-C(4)-C(5) bridge in 1 required that the terminal double bond activation pathway proceed by an alternative, energetically more-demanding pathway than that observed for 7. Ramifications of the decreased reactivity noted for 1 are to allow other functional groups (i.e., the C(1)-triol moiety) in the antibiotic to have important catalytic roles in the drug modification processes and to permit thiolate species (the proposed biological targets?) to effectively compete with other nucleophiles for 2.