(+/-)-2-oxo-cis-decahydro-1H-benzocycloheptene | 13837-39-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-2-oxo-cis-decahydro-1H-benzocycloheptene
• 英文别名: (+/-)-2-Oxo-cis-decahydro-1H-benzocyclohepten；(4aR,9aS)-1,2,4,4a,5,6,7,8,9,9a-decahydrobenzo[7]annulen-3-one
• CAS: 13837-39-3；16613-60-8；92286-89-0
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: MUAXSDQDUKMMCE-VHSXEESVSA-N

物化性质

• 沸点：
  255.4±8.0 °C(Predicted)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (+/-)-2-oxo-cis-decahydro-1H-benzocycloheptene 在 sodium tetrahydroborate 作用下， 生成 Toluene-4-sulfonic acid (4aR,9aS)-(decahydro-benzocyclohepten-2-yl) ester
  参考文献：
  名称：

  Transannular reactions of cycloalkenes, cycloalkadienes and cycloalkatrienes. 16. Photocyclization of cyclononene and cycloundecene

  摘要：

  Irradiation of cyclononene (7b) and cycloundecene (7d) in pentane afforded cis-bicyclo[4.3.0]nonane (10b) and cis-bicyclo[6.3.0]undecane (10d), respectively. Small amounts of the fragmentation products 1-undecene (14d) and 1-undecyne (15d) were also obtained from cycloundecene (7d). The photobehavior of the series of medium- and large-ring alkenes 7a-e is compared. Aside from E reversible Z isomerization, the principal pathway in each case involves rearrangement of the pi,R(3s) excited state to the cycloalkylidene intermediate 8, which undergoes predominant, if not exclusive, 1,5-transannular insertion to afford the corresponding cis-bicyclo[n.3.0]alkane (10). The cycloalkylidenes 8 formed in this way exhibit behavior somewhat different from those generated by other methods. The possible contributory role of carbene intermediates derived from pi,R(3s) excited states in E revesible Z photoisomerization of acyclic alkenes is also discussed.

  DOI：

  10.1021/jo00013a041
• 作为产物：
  描述：

  6,7,8,9-tetrahydro-5H-benzocyclohepten-2-ol 在 钌 作用下， 生成 (+/-)-2-oxo-cis-decahydro-1H-benzocycloheptene
  参考文献：
  名称：

  Granger et al., Bulletin de la Societe Chimique de France, 1963, p. 202

  摘要：

  DOI：

文献信息

• The first metal-catalyzed intramolecular [5+2] cycloadditions of vinylcyclopropanes and alkenes: Scope, stereochemistry, and asymmetric catalysis
  作者：Paul A. Wender、Craig O. Husfeld、Elke Langkopf、Jennifer A. Love、Norbert Pleuss

  DOI：10.1016/s0040-4020(98)00355-x

  日期：1998.6

  The first studies of the metal-catalyzed [5+2] cycloadditions of vinylcyclopropanes and alkenes are described. These reactions proceed with exceptional diastereoselectivity and in good to excellent yields. The effect of tether and substituent variations are examined. In addition, preliminary studies show that enantioselective cycloadditions can be achieved through the use of catalysts modified with

  描述了对金属催化的乙烯基环丙烷和烯烃的[5 + 2]环加成反应的初步研究。这些反应以异常的非对映选择性进行，并以良好至极好的收率进行。检查了系链和取代基变化的影响。此外，初步研究表明，通过使用经手性膦配体改性的催化剂，可以实现对映选择性环加成反应。这种新颖，通用，有效的方法为合成具有结构和医学意义的多种产品提供了一种根本上新的方法。
• Granger,R. et al., Bulletin de la Societe Chimique de France, 1971, p. 2662 - 2669
  作者：Granger,R. et al.

  DOI：——

  日期：——
• Zur Kenntnis des Kohlenstoffringes. Über cis-3.4-Polymethylen-cyclohexanone
  作者：V. Prelog、L. Ruzicka、O. Metzler

  DOI：10.1002/hlca.19470300663

  日期：1947.10.15
• Granger,R. et al., Bulletin de la Societe Chimique de France, 1973, p. 570 - 577
  作者：Granger,R. et al.

  DOI：——

  日期：——
• Transannular reactions of cycloalkenes, cycloalkadienes and cycloalkatrienes. 16. Photocyclization of cyclononene and cycloundecene
  作者：Guenter Haufe、Mark W. Tubergen、Paul J. Kropp

  DOI：10.1021/jo00013a041

  日期：1991.6

  Irradiation of cyclononene (7b) and cycloundecene (7d) in pentane afforded cis-bicyclo[4.3.0]nonane (10b) and cis-bicyclo[6.3.0]undecane (10d), respectively. Small amounts of the fragmentation products 1-undecene (14d) and 1-undecyne (15d) were also obtained from cycloundecene (7d). The photobehavior of the series of medium- and large-ring alkenes 7a-e is compared. Aside from E reversible Z isomerization, the principal pathway in each case involves rearrangement of the pi,R(3s) excited state to the cycloalkylidene intermediate 8, which undergoes predominant, if not exclusive, 1,5-transannular insertion to afford the corresponding cis-bicyclo[n.3.0]alkane (10). The cycloalkylidenes 8 formed in this way exhibit behavior somewhat different from those generated by other methods. The possible contributory role of carbene intermediates derived from pi,R(3s) excited states in E revesible Z photoisomerization of acyclic alkenes is also discussed.