(+)-(1R,4R,5R,6R)-5-exo,6-exo-(isopropylidenedioxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptan-2-one | 149233-65-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(1R,4R,5R,6R)-5-exo,6-exo-(isopropylidenedioxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptan-2-one
• 英文别名: (1R,2R,6R,7R)-2,4,4,7-tetramethyl-3,5,10-trioxatricyclo[5.2.1.02,6]decan-8-one
• CAS: 149233-65-8
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: YHKBYZSRXQYAPQ-YKDSUIRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(1R,4R,5R,6R)-5-exo,6-exo-(isopropylidenedioxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptan-2-one 在 甲醇 、 碳酸氢钠 、 间氯过氧苯甲酸 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 (-)-(1S,4R,5R,6R,7R)-6-exo,7-exo-(isopropylidenedioxy)-1,4-endo,6-endo-trimethyl-2,8-dioxabicyclo<3.2.1>octan-3-one
  参考文献：
  名称：

  Total asymmetric synthesis of polypropionate fragments and doubly branched heptono-1,4-lactones

  摘要：

  2-Cyano-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1'R)-camphanate ((+)-3)and (+)-(1R,4R)-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ((+)-4) were obtained readily from 3,4-dimethylfuran. (+)-3 was converted into 2,7-dideoxy-2,4-di-C-methyl-L-glycero- and D-glycero-L-altro-heptono-1,4-lactone ((+)-17) and ((+)-18).

  DOI：

  10.1016/s0040-4039(00)60444-6
• 作为产物：
  描述：

  2,4-二甲基呋喃 在 甲醇 、 四氧化锇 、 聚合甲醛 、 potassium carbonate 、 对甲苯磺酸 、 N-甲基吗啉氧化物 、 zinc(II) iodide 作用下， 以 水 、 丙酮 为溶剂， 反应 51.75h， 生成 (+)-(1R,4R,5R,6R)-5-exo,6-exo-(isopropylidenedioxy)-1,5-endo-dimethyl-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Total asymmetric synthesis of polypropionate fragments and doubly branched heptono-1,4-lactones

  摘要：

  2-Cyano-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1'R)-camphanate ((+)-3)and (+)-(1R,4R)-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ((+)-4) were obtained readily from 3,4-dimethylfuran. (+)-3 was converted into 2,7-dideoxy-2,4-di-C-methyl-L-glycero- and D-glycero-L-altro-heptono-1,4-lactone ((+)-17) and ((+)-18).

  DOI：

  10.1016/s0040-4039(00)60444-6

文献信息

• Synthesis of Polypropionate Fragments Containing Tertiary-Alcohol Moieties. Cross-aldolisations with lithium enolates of 7-oxabicyclo[2.2.1]heptan-2-one derivatives
  作者：Philippe Kernen、Pierre Vogel

  DOI：10.1002/hlca.19950780205

  日期：1995.3.22

  into (−)-(3R,4R,5R,6S)-3,4:5,7-bis(isopropylidenedioxy)-4,6-dimethylheptan-2-one ((−)-22), and into (+)-(2R,3R,4R,5S,6S)-3,4:5,6-bis(isopropylidenedioxy)-2,4-dimethylheptanal ((+)-34). Condensation of ((+)-34 with the lithium enolate of (−)-(1R,4R,5S,6R)-6-exo-[(tert-butyl)dimethylsilyloxy]-1,5-endo-dimethyl-7-oxabicyclo[2.2.1] heptan-2-one ((−)-38; derived from (+)-1) gave a 3:2 mixture of aldols (+)-39

  的狄尔斯-阿德耳2,4-二甲基呋喃的加成物1-氰基乙烯基（1' - [R）-camphanate（（+） - （1 - [R，2小号，4 - [R）-2-外型-氰基-1,5-二甲基7-氧杂二环[2.2.1]庚-5-烯-2-内型-基（1' - [R）-camphanate（（+） - 1））转化为（+） - 2,7-二脱氧-2,4- -di- C-甲基-L-甘油-（（+）- 6）和-D-甘油-L- altro-庚酮-1,4-内酯（（+）- 7），变成（-）-（3 [R，4 - [R，5 - [R，6小号）-3,4：5,7-双（异丙基二烯二氧基）-4,6-二甲基庚-2--2-（（-）- 22），并成（+）-（2 R，3 R，4 R，5 S，6 S）-3,4：5,6-双（异丙基二烯二氧基）-2,4-二甲基庚醛（（+）- 34）。（（+）- 34与（-）-（1 R，4 R，5 S，6 R）-6- exo
• Reductive Oxa Ring Opening of 7-Oxabicyclo[2.2.1]heptan-2-ones. Synthesis of C-.alpha.-Galactosides of Carbapentopyranoses
  作者：Janine Cossy、Jean-Luc Ranaivosata、Veronique Bellosta、Jacek Ancerewicz、Rafael Ferritto、Pierre Vogel

  DOI：10.1021/jo00131a007

  日期：1995.12

  Photoinduced electron transfer from Et(3)N to 7-oxabicyclo[2.2.1]heptan-2-ones can generate the corresponding 3-hydroxycyclohexanone derivatives. The method has been applied to the synthesis of C-alpha-D-galactopyranosides of carbapentopyranoses. Radical alpha-D-galactosidation of (+/-)-(1RS,4RS,5RS, 6RS)-6-endo-methoxy-3-methylidene-5-exo-(phenylseleno)-7-oxabicyclo[2.2.l]hept-2-one ((+)-51) followed by seleno-Pummerer rearrangement and reduction with Bu(3)SnH gave (+)- (1R,2S,3S,4R,6R)-((+)-58) and (+)-(1S,2R,3R,4S,6S)-3-endo-methoxy-5-oxo-6-endo-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]-7-oxabicyclo[2.2.1]hept-2-endo-yl acetate ((+)-59), which were separated by column chromatography. Irradiation (254 nn) in the presence of Et(3)N gave (+)-(1S,2R,3R,6R)-((+)-60) and (+)-(1R,2S,3S,6S)-2-hydroxy-6-methoxy-4-oxo-3-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]cyclohexyl acetate (+)-61, respectively. NaBH4 reduction and acetylation provided (+)-(1S,2S,3R,4R,5R)-((+)-62) and (+)-(1R,2R,3S,4S,5S)-5-methoxy-2-[(2',3',4',6'-tetra-0-acetyl-alpha-D-galactopyranosyl)methyl]cyclohexa-1,3,4-triyl triacetate ((+)-64).
• Total asymmetric synthesis of polypropionate fragments and doubly branched heptono-1,4-lactones
  作者：Philippe Kernen、Pierre Vogel

  DOI：10.1016/s0040-4039(00)60444-6

  日期：1993.4

  2-Cyano-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1'R)-camphanate ((+)-3)and (+)-(1R,4R)-1,5-dimethyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ((+)-4) were obtained readily from 3,4-dimethylfuran. (+)-3 was converted into 2,7-dideoxy-2,4-di-C-methyl-L-glycero- and D-glycero-L-altro-heptono-1,4-lactone ((+)-17) and ((+)-18).