(2RS, 5SR)-2,5-dimethyl-8-oxabicyclo<4.3.0>nona-1(6),3-dien-7-one | 86739-67-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (2RS, 5SR)-2,5-dimethyl-8-oxabicyclo<4.3.0>nona-1(6),3-dien-7-one
• 英文别名: cis-4,7-dimethyl-4,7-dihydrophthalide；(4S,7R)-4,7-dimethyl-4,7-dihydro-3H-2-benzofuran-1-one
• CAS: 86739-67-5；134390-25-3
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: IHUMHGWGBISHEG-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.68
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2RS, 5SR)-2,5-dimethyl-8-oxabicyclo<4.3.0>nona-1(6),3-dien-7-one 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲苯 为溶剂， 反应 14.0h， 生成 4,7-Dimethylphthalide
  参考文献：
  名称：

  (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry

  摘要：

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.

  DOI：

  10.1021/jo00013a033
• 作为产物：
  描述：

  (2-carbomethoxy-3,6-dimethyl-1,4-cyclohexadienyl)methyl 2-nitrobenzenesulfenate 在 哌啶 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以85%的产率得到(2RS, 5SR)-2,5-dimethyl-8-oxabicyclo<4.3.0>nona-1(6),3-dien-7-one
  参考文献：
  名称：

  (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry

  摘要：

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.

  DOI：

  10.1021/jo00013a033

文献信息

• Bailey, Stephen J.; Thomas, Eric J.; Vather, Sunil M., Journal of the Chemical Society. Perkin transactions I, 1983, p. 851 - 860
  作者：Bailey, Stephen J.、Thomas, Eric J.、Vather, Sunil M.、Wallis, John

  DOI：——

  日期：——
• PADWA, ALBERT;BULLOCK, WILLIAM H.;NORMAN, BRYAN H.;PERUMATTAM, JOHN, J. ORG. CHEM., 56,(1991) N3, C. 4252-4259
  作者：PADWA, ALBERT、BULLOCK, WILLIAM H.、NORMAN, BRYAN H.、PERUMATTAM, JOHN

  DOI：——

  日期：——