(1R,4R)-(+)-bicyclo<2.2.2>oct-7-ene-2,5-dione | 84366-54-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4R)-(+)-bicyclo<2.2.2>oct-7-ene-2,5-dione
• 英文别名: (+)-5,7-dioxobicyclo<2.2.2>oct-2-ene；(1R,4R)-bicyclo[2.2.2]oct-7-en-2,5-dione；(1R,4R)-bicyclo[2.2.2]oct-7-ene-2,5-dione
• CAS: 84366-54-1
• 化学式: C₈H₈O₂
• 分子量: 136.15
• InChiKey: RLWFLNMCQMZCJQ-WDSKDSINSA-N

物化性质

• 熔点：
  97-100 °C
• 沸点：
  278.5±40.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  phenylmagnesium bromide 、 (1R,4R)-(+)-bicyclo<2.2.2>oct-7-ene-2,5-dione 以 四氢呋喃 、 乙醚 为溶剂， 以23%的产率得到(1R,2S,4R,5S)-2,5-diphenylbicyclo[2.2.2]oct-7-ene-2,5-diol
  参考文献：
  名称：

  Bicyclo[2.2.2]octane-derived chiral ligands—synthesis and application of BODOLs in the asymmetric reduction of acetophenone with catecholborane

  摘要：

  An improved synthetic route to the bicyclo[2.2.2]octane-2,6-diol ligands (2,6-BODOLS) allowed an increased structural variation of the ligand side-arm. The addition of aromatic or vinylic Grignard reagents to hydroxyketone 1 was highly selective and ligands 3f-3I were isolated in 84-97% yield. The addition of alkyl Grignard reagents containing beta-hydrogens resulted in lower yields (13-71%) due to competing ketone reduction. A number of 2,5-BODOLs were synthesized using a similar methodology. The ligands, together with Ti(OiPr)(4), were tested in the asymmetric reduction of acetophenone with catecholborane (up to 98% ee). 1-Naphthyl-BODOL 3i was employed as an allylboration reagent to benzaldehyde together with Sc(OTf)(3), resulting in (1S)-1-phenyl-3-buten-1-ol in 80% ee. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.07.006
• 作为产物：
  描述：

  3a,6,7,7alpha-四氢-4,7-乙桥异苯并呋喃-1,3,5,9(4H)-四酮 在 吡啶 、 水 作用下， 以 水 为溶剂， 反应 8.0h， 生成 (1R,4R)-(+)-bicyclo<2.2.2>oct-7-ene-2,5-dione
  参考文献：
  名称：

  Synthesis and chiroptical properties of (1S)-[2,5-2H2]bicyclo[2.2.2]octa-2,5,7-triene (2,5-dideuteriobarrelene)

  摘要：

  DOI：

  10.1021/jo00244a023

文献信息

• Total synthesis of (-)-coriolin
  作者：Martin. Demuth、Peter. Ritterskamp、Eva. Weigt、Kurt. Schaffner

  DOI：10.1021/ja00274a050

  日期：1986.7

  Synthese en 14 etapes a partir de la bicyclo [2.2.2] octene-7 dione-2,5(±) avec comme etape cle un rearrangement photochimique oxadi-π-methane

  合成这些 en 14 etapes a partir de la bicyclo [2.2.2] octene-7 dione-2,5(±) avec comme etape cle un 重排 photochimique oxadi-π-methane
• Synthesis and chiroptical properties of 5,7-dioxobicyclo[2.2.2]oct-2-ene and bicyclo[2.2.2]octane-2,5-dione
  作者：Richard K. Hill、Gerald H. Morton、John R. Peterson、James A. Walsh、Leo A. Paquette

  DOI：10.1021/jo00350a019

  日期：1985.12
• TODA, FUMIO;TANAKA, KOICHI, CHEM. EXPRESS., 4,(1989) N, C. 439-442
  作者：TODA, FUMIO、TANAKA, KOICHI

  DOI：——

  日期：——
• HILL, R. K.;MORTON, G. H.;PETERSON, J. R.;WALSH, J. A.;PAQUETTE, L. A., J. ORG. CHEM., 1985, 50, N 26, 5528-5533
  作者：HILL, R. K.、MORTON, G. H.、PETERSON, J. R.、WALSH, J. A.、PAQUETTE, L. A.

  DOI：——

  日期：——
• LIGHTNER, DAVID A.;PAQUETTE, LEO A.;CHAYANGKOON, PAOCHAI;LIN, HO-SHEN;PET+, J. ORG. CHEM., 53,(1988) N 9, 1969-1973
  作者：LIGHTNER, DAVID A.、PAQUETTE, LEO A.、CHAYANGKOON, PAOCHAI、LIN, HO-SHEN、PET+

  DOI：——

  日期：——