allyl 2-(3,3-dimethylbutyl)-3-<(trimethylsilyl)oxy>hepta-2,6-dienoate | 142762-95-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: allyl 2-(3,3-dimethylbutyl)-3-<(trimethylsilyl)oxy>hepta-2,6-dienoate
• 英文别名: prop-2-enyl (2Z)-2-(3,3-dimethylbutyl)-3-trimethylsilyloxyhepta-2,6-dienoate
• CAS: 142762-95-6
• 化学式: C₁₉H₃₄O₃Si
• 分子量: 338.563
• InChiKey: SMMQGCQVHUQEQQ-MSUUIHNZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  23
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.63
• 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：

  allyl 2-(3,3-dimethylbutyl)-3-<(trimethylsilyl)oxy>hepta-2,6-dienoate 在 N-碘代丁二酰亚胺 、 tris(dibenzylideneacetone)dipalladium (0) 、 六正丁基二锡 、 1,2-双(二苯基膦)乙烷 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 1.75h， 生成 4-(3,3-dimethylbutyl)-1,8-nonadien-5-one
  参考文献：
  名称：

  Total synthesis of (.+-.)-velloziolone.

  摘要：

  The first total synthesis of the 9,10-seco-kaurene velloziolone (3) has been accomplished using an atom transfer tandem free-radical cyclization to prepare the 6-methylenebicyclo[3.2.1]octan-2-one moiety. The known diol 11 is converted to iodo acetate 10 in three steps. Alkylation of beta-keto ester 22 with 10 affords 33 that is converted to alpha-iodo ketone 7 in one pot by silylation, followed by palladium-catalyzed decarboxylation to give the tetra-substituted silyl enol ether regiospecifically and iodination of the enol ether. Atom transfer cyclization at 150-degrees-C, but not at 25 or 85-degrees-C, provides a mixture of bicyclic iodides. Elimination of HI and hydrolysis of the acetate furnishes velloziolone.

  DOI：

  10.1021/jo00044a024
• 作为产物：
  描述：

  三甲基氯硅烷 、 allyl 2-(3,3-dimethylbutyl)-3-oxohept-6-enoate 在 三乙胺 、 sodium iodide 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以97%的产率得到allyl 2-(3,3-dimethylbutyl)-3-<(trimethylsilyl)oxy>hepta-2,6-dienoate
  参考文献：
  名称：

  Total synthesis of (.+-.)-velloziolone.

  摘要：

  The first total synthesis of the 9,10-seco-kaurene velloziolone (3) has been accomplished using an atom transfer tandem free-radical cyclization to prepare the 6-methylenebicyclo[3.2.1]octan-2-one moiety. The known diol 11 is converted to iodo acetate 10 in three steps. Alkylation of beta-keto ester 22 with 10 affords 33 that is converted to alpha-iodo ketone 7 in one pot by silylation, followed by palladium-catalyzed decarboxylation to give the tetra-substituted silyl enol ether regiospecifically and iodination of the enol ether. Atom transfer cyclization at 150-degrees-C, but not at 25 or 85-degrees-C, provides a mixture of bicyclic iodides. Elimination of HI and hydrolysis of the acetate furnishes velloziolone.

  DOI：

  10.1021/jo00044a024

文献信息

• Total synthesis of (.+-.)-velloziolone.
  作者：Barry B. Snider、Brad O. Buckman

  DOI：10.1021/jo00044a024

  日期：1992.8

  The first total synthesis of the 9,10-seco-kaurene velloziolone (3) has been accomplished using an atom transfer tandem free-radical cyclization to prepare the 6-methylenebicyclo[3.2.1]octan-2-one moiety. The known diol 11 is converted to iodo acetate 10 in three steps. Alkylation of beta-keto ester 22 with 10 affords 33 that is converted to alpha-iodo ketone 7 in one pot by silylation, followed by palladium-catalyzed decarboxylation to give the tetra-substituted silyl enol ether regiospecifically and iodination of the enol ether. Atom transfer cyclization at 150-degrees-C, but not at 25 or 85-degrees-C, provides a mixture of bicyclic iodides. Elimination of HI and hydrolysis of the acetate furnishes velloziolone.