(+)-(1R,4R)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one-(2,4,6-triisopropylbenzene-sulfonylhydrazone) | 153829-38-0

• 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: (+)-(1R,4R)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one-(2,4,6-triisopropylbenzene-sulfonylhydrazone)
• 英文别名: camphor 2,4,6-triisopropylbenzenesulfonylhydrazone；2,4,6-tri(propan-2-yl)-N-[(E)-[(1R,4R)-1,7,7-trimethyl-2-bicyclo[2.2.1]heptanylidene]amino]benzenesulfonamide
• CAS: 153829-38-0
• 化学式: C₂₅H₄₀N₂O₂S
• 分子量: 432.671
• InChiKey: YKFIGPHOAFYJHB-SIUMHDTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  66.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(1R,4R)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one-(2,4,6-triisopropylbenzene-sulfonylhydrazone) 在 potassium hydrogensulfate 、 仲丁基锂 作用下， 反应 5.33h， 生成 (1R,5R,8R,9S,11S)-1,5,14,14,15,15-hexamethylpentacyclo<9.2.1.15,8.02,10.04,9>pentadeca-3,Δ2,10-diene
  参考文献：
  名称：

  On the structural features of the chiral organometallic Lewis-acid catalyst “(dibornacyclopentadienyl)zirconiumtrichloride”

  摘要：

  2-Bornenyllithium (3) was prepared from camphor by a variant of the Shapiro reaction and then reacted with 0.5 molar equivalents of ethylformate to give the dibornenylcarbinol 4. Subsequent acid-catalyzed cyclization of 4 yielded ''dibornacyclopentadiene'' as a mixture of two diastereoisomers; their deprotonation with n-butyllithium produced a single ''dibornacyclopentadienyllithium'' reagent (6). Reaction of 6 with MCl4 (M = Zr, Hf, Ti) gave the chiral organometallic Lewis-acids ''(diborna-CP)MCl3''. ''(+)-(Dibornacyclopentadienyl)zirconiumtrichloride'' (7a) was characterized by X-ray diffraction. The molecular structure of 7a provides a basis for discussing the stereochemical characteristics of the enantioselective arene hydroxyalkylation process catalyzed by the optically active organometallic Lewis-acid ''(dibornacyclopentadienyl)zirconiumtrichloride''.

  DOI：

  10.1016/0022-328x(93)86061-l
• 作为产物：
  描述：

  白樟油 、 2,4,6-三异丙基苯磺酰基肼 在 盐酸 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以83%的产率得到(+)-(1R,4R)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one-(2,4,6-triisopropylbenzene-sulfonylhydrazone)
  参考文献：
  名称：

  On the structural features of the chiral organometallic Lewis-acid catalyst “(dibornacyclopentadienyl)zirconiumtrichloride”

  摘要：

  2-Bornenyllithium (3) was prepared from camphor by a variant of the Shapiro reaction and then reacted with 0.5 molar equivalents of ethylformate to give the dibornenylcarbinol 4. Subsequent acid-catalyzed cyclization of 4 yielded ''dibornacyclopentadiene'' as a mixture of two diastereoisomers; their deprotonation with n-butyllithium produced a single ''dibornacyclopentadienyllithium'' reagent (6). Reaction of 6 with MCl4 (M = Zr, Hf, Ti) gave the chiral organometallic Lewis-acids ''(diborna-CP)MCl3''. ''(+)-(Dibornacyclopentadienyl)zirconiumtrichloride'' (7a) was characterized by X-ray diffraction. The molecular structure of 7a provides a basis for discussing the stereochemical characteristics of the enantioselective arene hydroxyalkylation process catalyzed by the optically active organometallic Lewis-acid ''(dibornacyclopentadienyl)zirconiumtrichloride''.

  DOI：

  10.1016/0022-328x(93)86061-l

文献信息

• Unprecedented Formation of a Benzo[d]azepine by Acid-Catalyzed Cyclization of a Camphor-DerivedN-Formylenamine
  作者：Gerrit J. Meuzelaar、Anders Blom、Leendert Maat、Roger A. Sheldon

  DOI：10.1002/(sici)1099-0690(199902)1999:2<519::aid-ejoc519>3.0.co;2-r

  日期：1999.2

  A convenient synthesis of (–)-N-styryl-N-[2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-enyl)ethyl]formamide (2) was developed starting from natural (+)-camphor (3) via (–)-2-(bornen-2-yl)ethanol (6). Cyclization of the N-formylenamine 2 with the aid of 9-borabicyclo[3.3.1]non-9-yl triflate yielded a methanobridged octahydro-1H-benzo[d]azepine derivative.

  从天然（+）开始开发了一种方便的合成（-）- N-苯乙烯基-N- [2-（1,7,7-三甲基双环[2.2.1]庚-2-烯基）乙基]甲酰胺（2）的方法-（2-3）经由（–）-2-（冰片-2-基）乙醇（6）合成-樟脑。借助9-硼杂环[3.3.1]非-9-基三氟甲磺酸酯对N-甲酰亚胺2进行环化，生成甲亚甲基桥连的八氢-1 H-苯并[ d ] ze庚因衍生物。
• On the structural features of the chiral organometallic Lewis-acid catalyst “(dibornacyclopentadienyl)zirconiumtrichloride”
  作者：Gerhard Erker、Jutta Schamberger、Adolphus A.H. van der Zeijden、Stefan Dehnicke、Carl Krüger、Richard Goddard、Matthias Nolte

  DOI：10.1016/0022-328x(93)86061-l

  日期：1993.10

  2-Bornenyllithium (3) was prepared from camphor by a variant of the Shapiro reaction and then reacted with 0.5 molar equivalents of ethylformate to give the dibornenylcarbinol 4. Subsequent acid-catalyzed cyclization of 4 yielded ''dibornacyclopentadiene'' as a mixture of two diastereoisomers; their deprotonation with n-butyllithium produced a single ''dibornacyclopentadienyllithium'' reagent (6). Reaction of 6 with MCl4 (M = Zr, Hf, Ti) gave the chiral organometallic Lewis-acids ''(diborna-CP)MCl3''. ''(+)-(Dibornacyclopentadienyl)zirconiumtrichloride'' (7a) was characterized by X-ray diffraction. The molecular structure of 7a provides a basis for discussing the stereochemical characteristics of the enantioselective arene hydroxyalkylation process catalyzed by the optically active organometallic Lewis-acid ''(dibornacyclopentadienyl)zirconiumtrichloride''.