((Z)-(5S,12R)-12,14-Dihydroxy-4-thia-tricyclo[10.4.0.0^5,16]hexadeca-1,8,15-triene-6,10-diyn-15-yl)-carbamic acid methyl ester | 108212-78-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫吡喃类
• 英文名称: ((Z)-(5S,12R)-12,14-Dihydroxy-4-thia-tricyclo[10.4.0.0^5,16]hexadeca-1,8,15-triene-6,10-diyn-15-yl)-carbamic acid methyl ester
• 英文别名: methyl N-[(5S,8Z,12R)-12,14-dihydroxy-4-thiatricyclo[10.4.0.05,16]hexadeca-1,8,15-trien-6,10-diyn-15-yl]carbamate
• CAS: 108212-78-8
• 化学式: C₁₇H₁₅NO₄S
• 分子量: 329.376
• InChiKey: PEPVNGGQWPTISS-RLGOLZJISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  104
• 氢给体数：
  3
• 氢受体数：
  5

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  卡利奇霉素	calicheamicin γ1I	108212-75-5	C55H74IN3O21S4	1368.37

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 ((Z)-(5S,12R)-12,14-Dihydroxy-4-thia-tricyclo[10.4.0.0^5,16]hexadeca-1,8,15-triene-6,10-diyn-15-yl)-carbamic acid methyl ester 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 Acetic acid (Z)-(5S,12R)-14-acetoxy-15-(acetyl-methoxycarbonyl-amino)-4-thia-tricyclo[10.4.0.0^5,16]hexadeca-1,8,15-triene-6,10-diyn-12-yl ester
  参考文献：
  名称：

  Calichemicins, a novel family of antitumor antibiotics. 2. Chemistry and structure of calichemicin .gamma.1I

  摘要：

  DOI：

  10.1021/ja00245a051
• 作为产物：
  描述：

  卡利奇霉素 在 sodium tetrahydroborate 、 Dowex 50W-X₈ 、 碘甲烷 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 18.33h， 生成 ((Z)-(5S,12R)-12,14-Dihydroxy-4-thia-tricyclo[10.4.0.0^5,16]hexadeca-1,8,15-triene-6,10-diyn-15-yl)-carbamic acid methyl ester
  参考文献：
  名称：

  Calicheamicins, a novel family of antitumor antibiotics. 4. Structure elucidation of calicheamicins .beta.1Br, .gamma.1Br, .alpha.2I, .alpha.3I, .beta.1I, .gamma.1I, and .delta.1I

  摘要：

  The details of the structural assignment of the potent antitumor antibiotic, calicheamicin gamma-1I (6, C55H74IN3O21S4), is reported. Methanolysis studies on 6 and N-acetylcalicheamicin gamma-1I (8, C57H76IN3022S4) permitted the structural assignment of the glycosidic chain. Details of the spectral analysis supporting the assignments of the 3-O-methyl-alpha-L-rhamnopyranoside (D-ring) and the methyl 2,4-dideoxy-3-O-methyl-4-(N-acetyl-N-ethylamino)-a-L-xylopyranoside (E-ring) is reported. The structure of calicheamicinone (32, C18H17NO5S3), containing a bicyclo[7.3.1 ] tridec-9-ene-2,6-diyne system and a methyl trisulfide, was elucidated by a series of chemical degradation studies, which included an unexpected free radical cycloaromatization reaction. The presence of 4,6-dideoxy-4-(hydroxyamino)-beta-D-glucopyranoside (A-ring) and its N-O glycosidic linkage to the thio sugar (B-ring) was ascertained by X-ray crystallography of 24 (C36H40INO13S2), a degradation product of 6. The chemical structures of calicheamicins beta-1Br (1), gamma-1Br (2), alpha-2I (3), alpha-3I (4), beta-1I (5), and delta-1I (7) were assigned by correlating their H-1 and C-13 NMR data with that of calicheamicin gamma-1I. By tracking the biological activities of the degradation products, the enediyne system of calicheamicinone was shown to be essential for the DNA-damaging abilities of the calicheamicins. A mechanism whereby the enediyne could be triggered to cyclize via a 1,4-diyl, the putative DNA cleaving species, is proposed.

  DOI：

  10.1021/ja00029a030

文献信息

• Calichemicins, a novel family of antitumor antibiotics. 2. Chemistry and structure of calichemicin .gamma.1I
  作者：May D. Lee、Theresa S. Dunne、Conway C. Chang、George A. Ellestad、Marshall M. Siegel、George O. Morton、William J. McGahren、Donald B. Borders

  DOI：10.1021/ja00245a051

  日期：1987.5
• Calicheamicins, a novel family of antitumor antibiotics. 4. Structure elucidation of calicheamicins .beta.1Br, .gamma.1Br, .alpha.2I, .alpha.3I, .beta.1I, .gamma.1I, and .delta.1I
  作者：May D. Lee、Theresa S. Dunne、Conway C. Chang、Marshall M. Siegel、George O. Morton、George A. Ellestad、William J. McGahren、Donald B. Borders

  DOI：10.1021/ja00029a030

  日期：1992.1

  The details of the structural assignment of the potent antitumor antibiotic, calicheamicin gamma-1I (6, C55H74IN3O21S4), is reported. Methanolysis studies on 6 and N-acetylcalicheamicin gamma-1I (8, C57H76IN3022S4) permitted the structural assignment of the glycosidic chain. Details of the spectral analysis supporting the assignments of the 3-O-methyl-alpha-L-rhamnopyranoside (D-ring) and the methyl 2,4-dideoxy-3-O-methyl-4-(N-acetyl-N-ethylamino)-a-L-xylopyranoside (E-ring) is reported. The structure of calicheamicinone (32, C18H17NO5S3), containing a bicyclo[7.3.1 ] tridec-9-ene-2,6-diyne system and a methyl trisulfide, was elucidated by a series of chemical degradation studies, which included an unexpected free radical cycloaromatization reaction. The presence of 4,6-dideoxy-4-(hydroxyamino)-beta-D-glucopyranoside (A-ring) and its N-O glycosidic linkage to the thio sugar (B-ring) was ascertained by X-ray crystallography of 24 (C36H40INO13S2), a degradation product of 6. The chemical structures of calicheamicins beta-1Br (1), gamma-1Br (2), alpha-2I (3), alpha-3I (4), beta-1I (5), and delta-1I (7) were assigned by correlating their H-1 and C-13 NMR data with that of calicheamicin gamma-1I. By tracking the biological activities of the degradation products, the enediyne system of calicheamicinone was shown to be essential for the DNA-damaging abilities of the calicheamicins. A mechanism whereby the enediyne could be triggered to cyclize via a 1,4-diyl, the putative DNA cleaving species, is proposed.