anti-2,3,3,4-tetramethyltricyclo<3.3.0.0^2,4>octane | 172745-89-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: anti-2,3,3,4-tetramethyltricyclo<3.3.0.0^2,4>octane
• 英文别名: (1R,2R,4S,5S)-2,3,3,4-tetramethyltricyclo[3.3.0.02,4]octane
• CAS: 172745-89-0
• 化学式: C₁₂H₂₀
• 分子量: 164.291
• InChiKey: GQACMROBZVSVCB-SKWLPYGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  anti-2,3,3,4-tetramethyltricyclo<3.3.0.0^2,4>octane 在 2,6-二叔丁基吡啶 、 tris-(4-bromophenyl)aminium hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 以97%的产率得到2,3,4,4-tetramethylbicyclo[3.3.0]oct-2-ene radical cation
  参考文献：
  名称：

  Diastereo- and Regioselective Synthesis of Diquinanes and Related Systems from Tricyclo[3.3.0.02,4]octanes by Chemical Electron Transfer (CET)

  摘要：

  提供了一种通过三环[3.3.0.02,4]辛烷的单电子氧化和随后的立体控制重排合成二喹烷的新合成方法。后者化合物可通过酸催化异吡唑环加成，随后氢化和分子氮的光排出方便地获得。三环辛烷的氧化重排催化且清洁地进行，区域和立体选择性地得到相应的二喹烷。

  DOI：

  10.1055/s-1995-4072
• 作为产物：
  描述：

  (1α,4α,4aα,7aα)-4,4a,5,6,7,7a-hexahydro-1,4,8,8-tetramethyl-1,4-methano-1H-cyclopenta[d]pyridazine 以 氘代甲苯 为溶剂， 反应 0.17h， 生成 anti-2,3,3,4-tetramethyltricyclo<3.3.0.0^2,4>octane
  参考文献：
  名称：

  环戊烷环化 DBH 型偶氮烷烃在三重环戊烷-1,3-二基双自由基环化过程中通过长程空间效应在光敏光脱氮中优先形成抗-Housane（保留）

  摘要：

  环戊烯和环戊烷退火的 DBH 型偶氮烷烃 1a 和 1b 的光解在单线态条件下（高温直接光解）主要提供了衍生物 2a 和 2b 数量相似的反向 housanes syn-2。在三重态条件下（低温直接或二苯甲酮敏化光解），光解导致保留的 housane anti-2 作为主要的非对映异构体，但 2a 的顺/反 housane 比率存在显着差异（38:62）对于 2b (6:94)。三线态途径的抗立体选择性的这种显着差异在环戊烷-1,3-二基三线态双自由基 3DR 环化过程中，环化环和嵴二甲基取代的亚甲基桥之间的长程空间相互作用在机械上合理化在 ISC 之后。相比之下，对于单线态过程，中间二氮烯基双自由基 1DZ 沿 SH2 途径（反转）的脱氮对这些远程空间效应非常不敏感。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,

  DOI：

  10.1002/ejoc.200390098

文献信息

• Influence of Ring Annelation on the Mode Selectivity of the Ionized Diazabicycloheptenes and Corresponding Housanes: An ESR and ENDOR Study
  作者：Fabian Gerson、Coşkun Şahin

  DOI：10.1002/1522-2675(20010613)84:6<1470::aid-hlca1470>3.0.co;2-w

  日期：2001.6.13

  The tricyclic azoalkanes, (1 alpha ,4 alpha ,4a alpha ,7a alpha)-4,4a,5,6,7,7a-hexahydro-1,4,8,8-tetramethyl-1,4-methano-1H-cyclopenta[d]pyridazine (1c), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,5,6,6a-pentahydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1d), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,6a-trihydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1e). and (1 alpha ,4 alpha ,4a alpha ,5a alpha)-4,4a,5,5a-tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropa[d]pyridazine (1f), as well as the corresponding housanes, the 2,3,3,4-tetramethyl-substituted tricyclo[3.3.0.0(2,4)]octane (2c). tricyclo[3.2.0.0(2,4)]heptane (2d), and tricyclo[ 3.2.0.0(2,4) ]hept-6-ene (2e), were subjected to gamma -irradiation in Freon matrices. The reaction products were identified with the use of ESR and. in part, ENDOR spectroscopy. As expected, the strain on the C-framework increases on going from the cyclopentane-annelated azoalkanes and housanes (1c and 2c) to those annelated by cyclobutane (1d and 2d), by cyclobutene (1e and 2e), and by cyclopropane (1f). Accordingly, the products obtained from Ic and 2c in all three Freons used, CFCl3, CF3CCl3, and CF2ClCFCl2, were the radical cations 3c(.+) and 2c(.+) of 2,3,4,4-tetramethylbicyclo[3.3.0]oct-2-ene and 2,3,3,4-tetramethylbicyclo[3,3,0]octane-2,4-diyl, respectively. In CFCl3, and CF3CCl3, matrices, Id and 2d yielded analogous products, namely the radical cations 3d(.+) and 2d(.+) of 2,3,4,4-tetramethylbicyclo[3.2.0]hept-2-ene and 2,3,3,4-tetramethylbicyclo[3.2.0]heptane-2,4-diyl. The radical cations 3c(.+) and 3d(.+) and 2c(.+) and 2d(.+) correspond to their non-annelated counterparts 3a(.+) and 3b(.+) and 2a(.+) and 2b(.+) generated previously under the same conditions from 2,3-diazabicyclo[2.2.1]hept-2-ene (1a) and bicyclo[2.1.0]pentane (2a), as well as from their 1,4-dimethyl derivatives (lb and 2b). However, in a CF2ClCFCl2 matrix, both ld and 2d gave the radical cation 4d(.+) of 2,3,3,4-tetramethylcyclohepta-1,4-diene. Starting from le and 2e, the radical cations 4e(.+) and 4e ' (.+) of the isomeric 1,2,7,7- and 1,6,7,7-tetramethylcyclohepta-1,3,5-trienes appeared as the corresponding products, while 1f was converted into the radical cation 4f(.+) of 1,5,6,6-tetramethylcyclohexa-1,4-diene which readily lost a proton to yield the corresponding cyclohexadienyl radical 4f(.). Reaction mechanisms leading to the pertinent radical cations are discussed.
• Diastereo- and Regioselective Synthesis of Diquinanes and Related Systems from Tricyclo[3.3.0.02,4]octanes by Chemical Electron Transfer (CET)
  作者：Waldemar Adam、Thomas Heidenfelder、Coskun Sahin

  DOI：10.1055/s-1995-4072

  日期：1995.9

  A new synthetic methodology for diquinanes by one-electron oxidation of tricyclo[3.3.0.02,4]octanes and subsequent stereocontrolled rearrangement is provided. The latter compounds are conveniently accessible through acid-catalyzed isopyrazole cycloaddition, followed by hydrogenation and photoextrusion of molecular nitrogen. The oxidative rearrangement of the tricyclooctanes proceeds catalytically and cleanly to afford regio- and diastereoselectively the corresponding diquinanes.

  提供了一种通过三环[3.3.0.02,4]辛烷的单电子氧化和随后的立体控制重排合成二喹烷的新合成方法。后者化合物可通过酸催化异吡唑环加成，随后氢化和分子氮的光排出方便地获得。三环辛烷的氧化重排催化且清洁地进行，区域和立体选择性地得到相应的二喹烷。
• Preferred Formation ofanti-Housane (Retention) in the Sensitized Photodenitrogenation of Cyclopentane-Annellated DBH-Type Azoalkanes through Long-Range Steric Effects in the Cyclization of the Triplet Cyclopentane-1,3-diyl Diradicals
  作者：Waldemar Adam、Manfred Diedering、Vicente Martí

  DOI：10.1002/ejoc.200390098

  日期：2003.2

  The photolysis of the cyclopentene- and cyclopentane-annellated DBH-type azoalkanes 1a and 1b affords under singlet conditions (high-temperature direct photolysis) predominantly the inverted housanes syn-2 in similar amounts for both derivatives 2a and 2b. Under triplet conditions (low-temperature direct or benzophenone-sensitized photolysis), the photolysis leads to the retained housane anti-2 as

  环戊烯和环戊烷退火的 DBH 型偶氮烷烃 1a 和 1b 的光解在单线态条件下（高温直接光解）主要提供了衍生物 2a 和 2b 数量相似的反向 housanes syn-2。在三重态条件下（低温直接或二苯甲酮敏化光解），光解导致保留的 housane anti-2 作为主要的非对映异构体，但 2a 的顺/反 housane 比率存在显着差异（38:62）对于 2b (6:94)。三线态途径的抗立体选择性的这种显着差异在环戊烷-1,3-二基三线态双自由基 3DR 环化过程中，环化环和嵴二甲基取代的亚甲基桥之间的长程空间相互作用在机械上合理化在 ISC 之后。相比之下，对于单线态过程，中间二氮烯基双自由基 1DZ 沿 SH2 途径（反转）的脱氮对这些远程空间效应非常不敏感。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,