(-)-quinolizinone | 142801-61-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (-)-quinolizinone
• 英文别名: (1S)-5-methoxy-10-azatetracyclo[8.7.0.02,7.011,15]heptadeca-2(7),3,5,11(15)-tetraen-16-one
• CAS: 142801-61-4
• 化学式: C₁₇H₁₉NO₂
• 分子量: 269.343
• InChiKey: KBRJFNHWAHLRLW-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-quinolizinone 在 hydrido(triphenylphosphine)copper(I) hexamer 、 甲基锂 作用下， 以 苯 为溶剂， 反应 4.7h， 生成 (-)-13-epi-aza-17-desoxo-12-oxoestrone methyl ether
  参考文献：
  名称：

  Chiral formamidines. The total asymmetric synthesis of (-)-8-azaestrone and related (-)-8-aza-12-oxo-17-desoxoestrone

  摘要：

  Attachment of the chiral formamidine moiety to 6-methoxy-1,2,3,4-tetrahydroisoquinoline afforded the key chiral, nonracemic precursor 8, upon which the azasteroid skeleton was constructed. Asymmetric alkylation with alpha-halo esters or beta-halo ethers gave 15 and 22, respectively, in high ee's. Cyclization, following enamine formation with cyclopentanedione or cyclopentanone, led to the chiral steroidal skeletons 6 and 5, respectively. The final stereocenters, leading to 8-azaestrone 4 with unnatural absolute configuration (antipodal), were accomplished by intramolecular alkylation of (+)-6b and subsequent reduction and ether cleavage. For the 12-oxosteroid 3, the methyl at C-13 was inserted by initial conjupte reduction of the enone 5 with a copper hydride reagent method) requiring the presence of a silyl chloride affording 21. The addition of methyl iodide to C-13 occurred after transforming the triethylsilyl enol ether, 21, to its lithium enolate. Stereochemical assignments for both azasteroids 3 and 4 were confirmed by spectroscopic means including circular dichroism curves.

  DOI：

  10.1021/jo00043a036
• 作为产物：
  描述：

  (6-Methoxy-1,2,3,4-tetrahydro-isoquinolin-1-yl)-acetic acid isopropyl ester 、 环戊酮 在 三氟乙酸 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以69%的产率得到(-)-quinolizinone
  参考文献：
  名称：

  Chiral formamidines. The total asymmetric synthesis of (-)-8-azaestrone and related (-)-8-aza-12-oxo-17-desoxoestrone

  摘要：

  Attachment of the chiral formamidine moiety to 6-methoxy-1,2,3,4-tetrahydroisoquinoline afforded the key chiral, nonracemic precursor 8, upon which the azasteroid skeleton was constructed. Asymmetric alkylation with alpha-halo esters or beta-halo ethers gave 15 and 22, respectively, in high ee's. Cyclization, following enamine formation with cyclopentanedione or cyclopentanone, led to the chiral steroidal skeletons 6 and 5, respectively. The final stereocenters, leading to 8-azaestrone 4 with unnatural absolute configuration (antipodal), were accomplished by intramolecular alkylation of (+)-6b and subsequent reduction and ether cleavage. For the 12-oxosteroid 3, the methyl at C-13 was inserted by initial conjupte reduction of the enone 5 with a copper hydride reagent method) requiring the presence of a silyl chloride affording 21. The addition of methyl iodide to C-13 occurred after transforming the triethylsilyl enol ether, 21, to its lithium enolate. Stereochemical assignments for both azasteroids 3 and 4 were confirmed by spectroscopic means including circular dichroism curves.

  DOI：

  10.1021/jo00043a036

文献信息

• Chiral formamidines. The total asymmetric synthesis of (-)-8-azaestrone and related (-)-8-aza-12-oxo-17-desoxoestrone
  作者：A. I. Meyers、Todd R. Elworthy

  DOI：10.1021/jo00043a036

  日期：1992.8

  Attachment of the chiral formamidine moiety to 6-methoxy-1,2,3,4-tetrahydroisoquinoline afforded the key chiral, nonracemic precursor 8, upon which the azasteroid skeleton was constructed. Asymmetric alkylation with alpha-halo esters or beta-halo ethers gave 15 and 22, respectively, in high ee's. Cyclization, following enamine formation with cyclopentanedione or cyclopentanone, led to the chiral steroidal skeletons 6 and 5, respectively. The final stereocenters, leading to 8-azaestrone 4 with unnatural absolute configuration (antipodal), were accomplished by intramolecular alkylation of (+)-6b and subsequent reduction and ether cleavage. For the 12-oxosteroid 3, the methyl at C-13 was inserted by initial conjupte reduction of the enone 5 with a copper hydride reagent method) requiring the presence of a silyl chloride affording 21. The addition of methyl iodide to C-13 occurred after transforming the triethylsilyl enol ether, 21, to its lithium enolate. Stereochemical assignments for both azasteroids 3 and 4 were confirmed by spectroscopic means including circular dichroism curves.