(1S,2R,6R,7R)-4,10-dioxatricyclo[5.2.1.02,6]dec-8-en-3-one | 104485-85-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: (1S,2R,6R,7R)-4,10-dioxatricyclo[5.2.1.02,6]dec-8-en-3-one
• CAS: 104485-85-0
• 化学式: C₈H₈O₃
• 分子量: 152.15
• InChiKey: KIAQKKYOUVIGII-MVIOUDGNSA-N

物化性质

• 沸点：
  338.0±42.0 °C(Predicted)
• 密度：
  1.366±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R,6R,7R)-4,10-dioxatricyclo[5.2.1.02,6]dec-8-en-3-one 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 12.0h， 以91%的产率得到<3aR-(3aα,4α,7α,7aα)>-hexahydro-4,7-epoxyisobenzofuran-1-(3H)-one
  参考文献：
  名称：

  Highly Enantioselective Ring Opening of Cyclic Meso-Anhydrides to Isopropyl Hemiesters with Ti−TADDOLates:  An Alternative to Hydrolytic Enzymes?

  摘要：

  The Lewis acid mediated transfer of an alkoxide ligand from the chiral ligand sphere of Ti-TADDOLate (1) to cyclic meso anhydrides to afford the corresponding hemiesters is described. By using this method a variety of structurally different anhydrides can be converted to isopropyl hemiesters with high enantioselectivities (enantiomer ratios up to 99:1). We have also investigated Lewis acidic titanium complexes, which differ from 1 in the chiral ligand or the alkoxide ligand that is transferred. Finally, a catalytic version, which allows the substoichiometric use of Ti-TADDOLate in the presence of stoichiometric amounts of Al(Oi-Pr)(3), is presented.

  DOI：

  10.1021/jo971731t
• 作为产物：
  描述：

  (1S,2S,3R,4R)-2-乙酰氧基甲基-3-羟甲基-7-氧杂双环[2.2.1]庚-5-烯 在 氢氧化钾 、 jones reagent 作用下， 以 丙酮 为溶剂， 反应 2.58h， 生成 (1S,2R,6R,7R)-4,10-dioxatricyclo[5.2.1.02,6]dec-8-en-3-one
  参考文献：
  名称：

  Asensio, Gregorio; Andreu, Cecilia; Marco, J. Alberto, Chemische Berichte, 1992, vol. 125, # 10, p. 2233 - 2238

  摘要：

  DOI：

文献信息

• Enantioselective Reduction of meso-Cyclic-1,2-dicarboxylic Anhydrides and 1,2-Dicarboximides: Asymmetric Synthesis of Bicyclic Lactones and Hydroxylactams.
  作者：Kenji MATSUKI、Hirozumi INOUE、Akihiko ISHIDA、Mikio TAKEDA、Masako NAKAGAWA、Tohru HINO

  DOI：10.1248/cpb.42.9

  日期：——

  Chiral bicyclic lactones (3, 8, 9) and bicyclic hydroxylactams (10-13) were synthesized by highly enantioselective reduction of meso-cyclic-1, 2-dicarboxylic anhydrides (1, 4) and meso-cyclic-1, 2-dicarboximides (2) with lithium aluminum hydride (LiAlH4)-alcohol(ROH)-(R)- or (S)-1, 1'-bi-2-naphthol complex [(R)- or (S)-BINAL-H(ROH)]. Treatment of the hydroxylactams (10-13) with triethylsilane (Et3SiH) and trifluoroacetic acid (CF3CO2H) gave chiral bicyclic lactams (14, 15) in quantitative yields. Removal of the N-4-methoxyphenyl group of the lactams (14, 15) with cerium(IV) ammonium nitrate (CAN) proceeded smoothly to give the corresponding N-unsubstituted lactams (16, 17) in high optical purity.

  手性双环内酯（3、8、9）和双环羟基内酰胺（10-13）是通过对meso-环状-1,2-二羧酸酐（1、4）和meso-环状-1,2-二羧酰胺（2）进行具有高对映选择性的还原反应，使用锂铝氢化物（LiAlH4）-醇（ROH）-（R）或（S）-1,1'-双-2-萘醇复合物[(R)或(S)-BINAL-H(ROH)]合成的。对羟基内酰胺（10-13）进行三乙基硅烷（Et3SiH）和三氟乙酸（CF3CO2H）的处理，得到了手性双环内酰胺（14、15），产率为定量。在高光学纯度下，用铈(IV)铵硝酸盐（CAN）顺利去除内酰胺（14、15）中的N-4-甲氧基苯基基团，得到相应的N-不取代内酰胺（16、17）。
• Stereoselective intramolecular michael addition induced by a thermolabile group: Synthesis of optically active five-membered oxygen-containing rings.
  作者：Robert Bloch、Matar Seck

  DOI：10.1016/s0040-4039(01)81062-5

  日期：1987.1

  A tandem Wittig-Michael reaction allows the stereoselective formation of the tricyclic compound from the chiral lactol . A retro Diels-Alder reaction leads to the dihydrofuran of high enantiomeric purity.

  串联的Wittig-Michael反应可以从手性乳糖醇立体选择性地形成三环化合物。逆向狄尔斯-阿尔德反应导致对映体纯度高的二氢呋喃。
• Highly enantioselective reduction of meso-1,2-dicarboxylic anhydrides
  作者：Kenji Matsuki、Hirozumi Inoue、Mikio Takeda

  DOI：10.1016/s0040-4039(00)77518-6

  日期：1993.2

  Optically active lactones (2a-2g) were synthesized by highly enantioselective reduction of readily available meso-1,2-dicarboxylic anhydrides (1a-1g) using lithium aluminum hydride -ethanol-1,1'-bi-2-naphthol complex (BINAL-H).
• Asymmetric catalytic reduction of meso-imides
  作者：Jahyo Kang、Jun Won Lee、Joo In Kim、Chongsuh Pyun

  DOI：10.1016/0040-4039(95)00728-u

  日期：1995.6

  A thiazazincolidine complex, 1, was shown to be an excellent catalyst for enantioselective reduction with bis(2,6-dimethylphenoxy)borane (BDMPB) of meso N-phenylimides in high ee to the corresponding hydroxy lactams, which were eventually converted to the corresponding lactones of high optical purity.
• Synthesis of both enantiomers of .gamma.-substituted .alpha.,.beta.-unsaturated .gamma.-lactones
  作者：R. Bloch、L. Gilbert

  DOI：10.1021/jo00229a031

  日期：1987.10