(4'ar,8'ac)-hexahydro-spiro[[1,3]dioxolane-2,7'-quinolin]-2'-one | 64908-35-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉类
• 英文名称: (4'ar,8'ac)-hexahydro-spiro[[1,3]dioxolane-2,7'-quinolin]-2'-one
• 英文别名: (4aS,8aS)-spiro[1,3,4,4a,5,6,8,8a-octahydroquinoline-7,2'-1,3-dioxolane]-2-one
• CAS: 64908-35-6；64908-38-9
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: QDDLDMMASJNRAU-BDAKNGLRSA-N

物化性质

• 熔点：
  192-193 °C(Solv: benzene (71-43-2); hexane (110-54-3))
• 沸点：
  416.3±40.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4'ar,8'ac)-hexahydro-spiro[[1,3]dioxolane-2,7'-quinolin]-2'-one 在 盐酸 、 sodium tetrahydroborate 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 5.0h， 生成 (4aS,7R,8aS)-7-hydroxy-1-methyl-3,4,4a,5,6,7,8,8a-octahydroquinolin-2-one
  参考文献：
  名称：

  Theoretical and Experimental Studies of Asymmetric Organozinc Additions to Benzaldehyde Catalyzed by Flexible and Constrained γ-Amino Alcohols

  摘要：

  The cis-decalin based gamma-amino alcohols, 1-5, were synthesized, resolved, and employed as catalysts in the addition of organozincs to benzaldehyde. Despite large facial differentiation in the RZn adducts of the ligands, the enantioselectivities were found to be moderate. Transition structure calculations were done using several quantum chemical methods to examine the underlying causes of the selectivity for three gamma-amino alcohols, 1, 2, and 3. The tricyclic mu-oxo (6/4/4), rather than the bicyclic six-membered (6/6), transition structures were found to explain the observed enantioselectivity for 2 and 3. MP2 calculations gave the best correlation to the experimental results compared to B3LYP and HIP calculations. The conformational flexibility of the chiral ligands was found to be an important factor in the selectivity.

  DOI：

  10.1021/jo0262210
• 作为产物：
  描述：

  2,7-Dioxo-1,2,3,4,4a,5,6,7-octahydroquinoline 在 rhodium on alumina 氢气 、 对甲苯磺酸 作用下， 以 乙醇 、 苯 为溶剂， 25.0 ℃ 、4.41 MPa 条件下， 生成 (4'ar,8'ac)-hexahydro-spiro[[1,3]dioxolane-2,7'-quinolin]-2'-one
  参考文献：
  名称：

  Momose,T. et al., Chemical and pharmaceutical bulletin, 1977, vol. 25, p. 1797 - 1802

  摘要：

  DOI：

文献信息

• Octahydro-7(1H)-quinolones. VII. A stereoselective synthesis of cis,trans-decahydro-3H,8H-benzo[i,j]quinolizine-3,8-dione.
  作者：TAKEFUMI MOMOSE、SHUJI UCHIDA、TAKESHI IMANISHI

  DOI：10.1248/cpb.27.215

  日期：——

  The conversion of 1-(3-chloropropyl)-cis-decahydroquinoline-2, 7-dione (3) into decahydro-3H, 8H-benzo [i, j] quinolizine-3, 8-diones (12a and 12b) was accomplished with retention of the parent stereochemistry. The stereochemistry of the tricyclic system was assigned from chemical and physical evidences. It was postulated that this successful ring closure in the cis ring system resulted from easy fulfilment of the stereoelectronic requirement, for intramolecular alkylation in 3, much reduced as compared to that for N-acrylyl-cis-octahydro-7 (1H)-quinolone (1b).

  将 1-(3-氯丙基)-顺式-十氢喹啉-2，7-二酮（3）转化为十氢-3H，8H-苯并 [i，j] 喹嗪-3，8-二酮（12a 和 12b）时，保留了母体的立体化学结构。三环系统的立体化学结构是根据化学和物理证据确定的。据推测，顺式环系统成功闭环的原因是容易满足 3 分子内烷基化的立体电子学要求，与 N-丙烯酰基-顺式-八氢-7(1H)-喹啉酮（1b）相比，该要求大大降低。
• Theoretical and Experimental Studies of Asymmetric Organozinc Additions to Benzaldehyde Catalyzed by Flexible and Constrained γ-Amino Alcohols
  作者：Manoranjan Panda、Puay-Wah Phuan、Marisa C. Kozlowski

  DOI：10.1021/jo0262210

  日期：2003.1.1

  The cis-decalin based gamma-amino alcohols, 1-5, were synthesized, resolved, and employed as catalysts in the addition of organozincs to benzaldehyde. Despite large facial differentiation in the RZn adducts of the ligands, the enantioselectivities were found to be moderate. Transition structure calculations were done using several quantum chemical methods to examine the underlying causes of the selectivity for three gamma-amino alcohols, 1, 2, and 3. The tricyclic mu-oxo (6/4/4), rather than the bicyclic six-membered (6/6), transition structures were found to explain the observed enantioselectivity for 2 and 3. MP2 calculations gave the best correlation to the experimental results compared to B3LYP and HIP calculations. The conformational flexibility of the chiral ligands was found to be an important factor in the selectivity.
• Momose,T. et al., Chemical and pharmaceutical bulletin, 1977, vol. 25, p. 1797 - 1802
  作者：Momose,T. et al.

  DOI：——

  日期：——