5-methyltricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-methyltricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one
• 英文别名: (1S,2R,6S,7R)-5-methyltricyclo[5.2.1.02,6]deca-4,8-dien-3-one
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: AEIHUQBARCBGLZ-OEIWMXHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-methyltricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one 在 air 、 lithium tri-t-butoxyaluminum hydride 作用下， 以 乙醚 为溶剂， 反应 5.0h， 生成 (1S,2R,5S,6R,7R,8R,10S)-5-methyl-9-oxatetracyclo[5.3.1.02,6.08,10]undecan-3-one
  参考文献：
  名称：

  Regio- and stereoselectivity of additions of organometallics to - and -tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones

  摘要：

  The regio- and stereoselectivity of the addition of selected organometallics to endo- and exo-tricyclodecadienones 12, 18 and 21 are described. RLi and R(2)Culi add with complete 1,2- and 1,4-regioselectivity, respectively, the additions of RMgX and RMgX/CuX are only slightly less selective. Additions to 12 and 21 occur from the convex exo-face only, irrespective of the nature of both reagent and substrate. In contrast, organometallic species add from both the concave and the convex face to tricyclic ester 18, with a selectivity that depends on the type of organometallic reagent. The observed stereoselectivities of the additions are rationalized by invoking steric control by the C-8-C-9 ethylene bridge in 12, by the C-10 methylene bridge in 21 and by both the C-8-C-9 ethylene bridge and the exo-ester function at C-2 in tricyclic ester 18.

  DOI：

  10.1016/s0040-4020(01)81817-2
• 作为产物：
  描述：

  exo-3-methyl-endo-tricyclo<5.2.1.0^2,6>deca-4,8-dien-endo-3-ol 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以63%的产率得到5-methyltricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one
  参考文献：
  名称：

  从双环戊二烯到α-cuparenone的对映体收敛路线

  摘要：

  通过采用脂肪酶催化的动力学水解方法，已设计出由双环戊二烯向α-cuparenone转化的正式对映体路线。

  DOI：

  10.1039/c39890000271

文献信息

• Oxidative Rearrangement of Cyclic Tertiary Allylic Alcohols with IBX in DMSO
  作者：Masatoshi Shibuya、Shinichiro Ito、Michiyasu Takahashi、Yoshiharu Iwabuchi

  DOI：10.1021/ol048210u

  日期：2004.11.1

  A practical and environmentally friendly method for oxidative rearrangement of five- and six-membered cyclic tertiary allylic alcohols to beta-disubstituted alpha,beta-unsaturated ketones by the IBX/DMSO reagent system is described. Several conventional protecting groups (e.g., Ac, MOM, and TBDPS) are compatible under the reaction conditions prescribed.

  描述了一种实用且环境友好的方法，该方法通过IBX / DMSO试剂系统将五元和六元环状叔烯丙基醇氧化重排为β-二取代的α，β-不饱和酮。在规定的反应条件下，几种常规的保护基团（例如Ac，MOM和TBDPS）是相容的。
• TEMPO/NaIO₄−SiO₂: A Catalytic Oxidative Rearrangement of Tertiary Allylic Alcohols to β-Substituted α,β-Unsaturated Ketones
  作者：Masatoshi Shibuya、Masaki Tomizawa、Yoshiharu Iwabuchi

  DOI：10.1021/ol801673r

  日期：2008.11.6

  The novel catalytic method for the oxidative rearrangement of tertiary allylic alcohols to beta-substituted alpha,beta-unsaturated ketones is described. TEMPO/NaIO4-SiO2 causes facile and efficient oxidative rearrangement of various acyclic substrates as well as medium-sized and macrocyclic substrates.

  描述了一种新的催化方法，用于将叔烯丙基醇氧化重排为β-取代的α，β-不饱和酮。TEMPO / NaIO4-SiO2导致各种无环底物以及中型和大环底物的便捷有效氧化重排。
• Nucleophilic additions to tricyclodecadienone epoxides. The Payne rearrangement of α,β-epoxycyclopentanols contained in a rigid tricyclic system
  作者：Paul P.M.A. Dols、Esther G. Arnouts、Johannes Rohaan、Antonius J.H. Klunder、Binne Zwanenburg

  DOI：10.1016/s0040-4020(01)87027-7

  日期：1994.3

  conditions and type of organometallic reagent. Reduction of 6 and 7 with lithium aluminum hydride yields the same tricyclic trans-1,3-diols 20. It is shown that reduction of 6 with lithium aluminum hydride proceeds via slow Payne rearrangement of its alkoxide 11b to inverted alkoxide 12b, followed by rapid addition of hydride to C4 from the exo-face.

  有机金属试剂添加区域选择性和立体选择性地从凸外型-面到的羰基官能团外-4,5- epoxytricyclodecenones 5和8，得到三环外-环氧内切醇的6和9分别。这些初始加合物可以进行佩恩重排，分别得到倒位的内-环氧-外-醇7和10。重排取决于底物，实验条件和有机金属试剂的类型。减少6和7与氢化铝锂产生相同的三环反-1,3-二醇20。结果表明，减少的6经由慢佩恩重排氢化铝锂进行其醇盐11B到倒醇盐12B，接着迅速加入氢化至C 4从外面取向。
• Bugel,J.-P. et al., Bulletin de la Societe Chimique de France, 1972, p. 4371 - 4374
  作者：Bugel,J.-P. et al.

  DOI：——

  日期：——
• TAKANO, SEIICHI;INOMATA, KOHEI;OGASAWARA, KUNIO, J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 271-272
  作者：TAKANO, SEIICHI、INOMATA, KOHEI、OGASAWARA, KUNIO

  DOI：——

  日期：——