(1S,2S,4R)-2-(2,6-Dimethoxy-phenyl)-1,3,3-trimethyl-bicyclo[2.2.1]heptan-2-ol | 189191-34-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2S,4R)-2-(2,6-Dimethoxy-phenyl)-1,3,3-trimethyl-bicyclo[2.2.1]heptan-2-ol
• 英文别名: (1S,2S,4R)-2-(2,6-dimethoxyphenyl)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 189191-34-2
• 化学式: C₁₈H₂₆O₃
• 分子量: 290.403
• InChiKey: WQYMJDRJMWGSQA-OCBCSQNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2S,4R)-2-(2,6-Dimethoxy-phenyl)-1,3,3-trimethyl-bicyclo[2.2.1]heptan-2-ol 在 氢溴酸 作用下， 以 溶剂黄146 为溶剂， 反应 24.0h， 以42%的产率得到(1R,4S,4aR,9bR)-1,2,3,4,4a,9b-hexahydro-9-hydroxy-1,4-methano-1,4a,9b-trimethyldibenzofuran
  参考文献：
  名称：

  串联Wagner-Meerwein重排-碳配位捕获在手性杂环系统形成中的作用

  摘要：

  邻位锂化的受保护苯胺和苯酚会从exo脸上排入除二烯酮中的排他性成分。相应的加合物在酸性条件下进行阳离子重排，然后用氨基，羟基或甲氧基取代基对新阳离子进行内部捕集，从而得到对映体纯的手性杂环体系。重排的性质取决于供体基团及其稳定正电荷的能力。对于氨基供体基团，由于Wagner-Meerwein重排而形成产物，而对于甲氧基供体基团，Nametkin重排是优选的途径。

  DOI：

  10.1016/s0040-4039(97)00271-2
• 作为产物：
  描述：

  (+)-葑酮 、 间苯二甲醚 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以68%的产率得到(1S,2S,4R)-2-(2,6-Dimethoxy-phenyl)-1,3,3-trimethyl-bicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  串联Wagner-Meerwein重排-碳配位捕获在手性杂环系统形成中的作用

  摘要：

  邻位锂化的受保护苯胺和苯酚会从exo脸上排入除二烯酮中的排他性成分。相应的加合物在酸性条件下进行阳离子重排，然后用氨基，羟基或甲氧基取代基对新阳离子进行内部捕集，从而得到对映体纯的手性杂环体系。重排的性质取决于供体基团及其稳定正电荷的能力。对于氨基供体基团，由于Wagner-Meerwein重排而形成产物，而对于甲氧基供体基团，Nametkin重排是优选的途径。

  DOI：

  10.1016/s0040-4039(97)00271-2

文献信息

• Tandem Wagner-Meerwein rearrangement-carbocation trapping in the formation of chiral heterocyclic ring systems
  作者：Scott M. Starling、Simone C. Vonwiller

  DOI：10.1016/s0040-4039(97)00271-2

  日期：1997.3

  cationic rearrangement followed by internal trapping of the new cation with amino, hydroxyl or methoxyl substituents to give enantiomerically pure chiral heterocyclic ring systems. The nature of the rearrangement is dependent on the donor group and its ability to stabilise a positive charge. With an amino donor group a product due to Wagner-Meerwein rearrangement is formed while with a methoxy donor group

  邻位锂化的受保护苯胺和苯酚会从exo脸上排入除二烯酮中的排他性成分。相应的加合物在酸性条件下进行阳离子重排，然后用氨基，羟基或甲氧基取代基对新阳离子进行内部捕集，从而得到对映体纯的手性杂环体系。重排的性质取决于供体基团及其稳定正电荷的能力。对于氨基供体基团，由于Wagner-Meerwein重排而形成产物，而对于甲氧基供体基团，Nametkin重排是优选的途径。
• Effect of Ortho Substituents on the Direction of 1,2-Migrations in the Rearrangement of 2-<i>exo</i>-Arylfenchyl Alcohols
  作者：Scott M. Starling、Simone C. Vonwiller、Joost N. H. Reek

  DOI：10.1021/jo972025v

  日期：1998.4.1

  A series of 8-exo-arylfenchyl alcohols (11a-k) was submitted to acid hydrolysis in EtOH/10 M HCl (2:1-1:1, v/v) or with trifluoromethanesulfonic acid (TfOH) (1 equiv) in CHCl3 under varying conditions. In all cases, initial formation of the cyclofenchene 12 took place, and after prolonged treatment with acid the reaction proceeded along one of two pathways depending on the nature of the aryl substituent. When the aryl substituent was o-NH2 11b or o-OH 11e, Wagner-Meerwein rearrangement took place to give a carbocationic intermediate 9 that was trapped by the N or O heteroatom to give (2R,4aR,9aR)-9-aza-2,4a-(10,10-dimethylmethano)-1,2,3,4,4a,9a-hexahydro-9a-methyl-9H-fluorene (3b) and (3R,4aR,9bR)-3,9b-(10,10-dimethylmethano)-1,2,3,4,4a,9b-hexahydro-4a-methyldibenzofuran (3c), respectively. In the case of 3c bearing an oxygen heteroatom, equilibration to give the thermodynamic product (1R,4S,4aR,9bR)-1,2,3,4,4a,9b-hexahydr-1,4-methano-1,4a,9b-trimethyldibenzofuran (4a), arising from Nametkin rearrangement, took place via the intermediate 8-fenchyl cation. In contrast, when the aryl substituent was o-OCH3 11f, direct conversion of the cyclofenchene to the Nametkin product 4a occurred with no detectable prior formation of the Wagner-Meerwein product. In the case of o-tolylfenchyl alcohol 11k, cyclofenchene formation was facile, but subsequent conversion to either the Wagner-Meerwein or Nametkin products was highly disfavored. The results indicate that ortho substitution disfavors Wagner-Meerwein rearrangement through adverse steric and electronic effects. However, when the ortho substituent is NH2 or OH it is proposed that anchimeric assistance provides an intermediate 15a that is stereoelectronically predisposed to Wagner-Meewein rearrangement.