1a-Acetyl-7-demethoxy-6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitomycin A | 134618-72-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1a-Acetyl-7-demethoxy-6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitomycin A
• 英文别名: 6-Demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitosane；6-demethyl-7,7-(ethylenedioxy)-6-(phenylseleno)mitosane；6-demethyl-6-phenylselenomitosane；[(4'S,6'S,7'R,8'S)-5'-acetyl-7'-methoxy-10',13'-dioxo-12'-phenylselanylspiro[1,3-dioxolane-2,11'-2,5-diazatetracyclo[7.4.0.02,7.04,6]tridec-1(9)-ene]-8'-yl]methyl carbamate
• CAS: 134618-72-7
• 化学式: C₂₄H₂₅N₃O₈Se
• 分子量: 562.438
• InChiKey: YQTHUDVXOIWYJM-NGOOXVDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.06
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  138
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1a-Acetyl-7-demethoxy-6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitomycin A 在 N-氯代丁二酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以29%的产率得到1a-Acetyl-6-chloro-7-demethoxy-6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitomycin A
  参考文献：
  名称：

  6-Demethyl-6-halo- and 6-Demethyl-6-thiomitomycins: Synthesis of Novel Mitomycin Derivatives Involving a Tandem Michael Addition/Retro-Mannich Reaction Sequence

  摘要：

  Synthesis of novel 6-demethyl-6-halomitomycins (3, 4, 6, and 7) and 6-demethyl-6-thiomitomycins (5 and 8) is described from key intermediates, namely, 6-demethyl-7,7-(ethylenedioxy)-6,6-dihalo- 6,7-dihydromitosanes (18 and 19) and 6-demethyl-7,7- (ethylenedioxy)-6,7-dihydro-6-thiomitosane (20), respectively. Compounds 18-20 were prepared through a tandem Michael addition and a retro-Mannich reaction sequence (N-halosuccinimide or cationic arylsulfenyl species in the presence of Et(2)NH) on 10.

  DOI：

  10.1021/jo00084a028
• 作为产物：
  描述：

  7,7-(Ethylenedioxy)-6-(phenylseleno)mitosane 在 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 正己烷 、 二氯甲烷 、 氯仿 为溶剂， 反应 3.17h， 生成 1a-Acetyl-7-demethoxy-6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-(phenylseleno)mitomycin A
  参考文献：
  名称：

  First synthesis of mitomycins completely labeled at the C-6-methyl by 13CH3 and CD3

  摘要：

  The C-6-methyl group of mitomycins was completely labeled with carbon-13 or deuterium for the first time. The synthesis was accomplished by the C-6-methylation of 6-demethyl-7,7-(ethylenedioxy)-6-(phenylseleno)mitosane 8 that was formed by a novel replacement of the methylene moiety of 6-demethyl-7,7-(ethylenedioxy)-6-methylenemitosane 10 by a phenylseleno group, and followed by conversion to the mitomycins. For the synthesis of 8, we found that selenenamide 11 is an excellent reagent for the replacement. We have also determined that the replacement proceeded via the addition of 11 to the methylene of 10 with a subsequent retro-Mannich reaction.

  DOI：

  10.1021/jo00056a022

文献信息

• An unusual replacement of a methylene moiety by a phenylseleno group. Synthesis of mitomycin C labelled at C-6 by 13CH3 and C2H3
  作者：Masaji Kasai、Hitoshi Arai、Yutaka Kanda

  DOI：10.1039/c39910000600

  日期：——

  A novel replacement of the C-6-methylene group of 7,7-ethylenedioxy-6-methylenemitosane by a phenylseleno group was employed to prepare a critical intermediate in the synthesis of mitomycin C labelled at C-6 by 13CH3 and C2H3.

  利用苯基硒基取代 7,7-ethylenedioxy-6-methylenemitosane 的 C-6-亚甲基这一新颖方法，制备了丝裂霉素 C 合成过程中的一个关键中间体，该中间体的 C-6 被 13CH3 和 C2H3 标记。
• Facile nucleophilic cleavage of selenide with dimedone. Synthesis of novel 6-demethylmitomycins
  作者：Hitoshi Arai、Masaji Kasai

  DOI：10.1021/jo00067a063

  日期：1993.7
• Synthesis and Antitumor Activity of Novel 6-Alkyl-6-demethylmitomycins
  作者：Hitoshi Arai、Yutaka Kanda、Tadashi Ashizawa、Makoto Morimoto、Katsushige Gomi、Motomichi Kono、Masaji Kasai

  DOI：10.1021/jm00038a009

  日期：1994.6

  A series of 6-alkyl-6-demethylmitomycins (1-5) was synthesized and evaluated for anticellular and antitumor activities. These novel compounds were prepared by Michael addition of various carbanion species to 6-demethyl-7,7-(ethylenedioxy)-6,7-dihydro-6-methylidenemitosane (6 and 9) followed by treatment with NH3 or MeOH/K2CO3. Alkylation at the C-6 position of 6-demethyl-6-selenide (7) was also useful for the alternative synthesis of 6-alkyl-6-demethylmitomycins. The antitumor activity of these derivatives was evalulated, and 6-demethyl-6-ethylmitomycin A (2a) was found to exhibit excellent activity against S-180 solid tumor in mice. The structure-activity relationship is also discussed.
• ARAI, HITOSHI;KASAI, MASAJI, J. LABELL. COMPOUNDS AND RADIOPHARM., 29,(1991) N, C. 903-908
  作者：ARAI, HITOSHI、KASAI, MASAJI

  DOI：——

  日期：——