allyl 2-(3,3-dimethylbutyl)-3-oxohept-6-enoate | 142762-94-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: allyl 2-(3,3-dimethylbutyl)-3-oxohept-6-enoate
• 英文别名: Prop-2-enyl 2-(3,3-dimethylbutyl)-3-oxohept-6-enoate
• CAS: 142762-94-5
• 化学式: C₁₆H₂₆O₃
• 分子量: 266.381
• InChiKey: GIAXFTPXNZQAEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  43.4
• 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-oxohept-6-enoate 在 N-碘代丁二酰亚胺 、 tris(dibenzylideneacetone)dipalladium (0) 、 六正丁基二锡 、 三乙胺 、 1,2-双(二苯基膦)乙烷 、 sodium iodide 作用下， 以 四氢呋喃 、 乙腈 、 苯 为溶剂， 反应 1.92h， 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：

  allyl 3-oxohept-6-enoate 、 (1S,5R)-6-Iodomethyl-bicyclo[3.2.1]octan-2-one 在 potassium hydride 作用下， 生成 allyl 2-(3,3-dimethylbutyl)-3-oxohept-6-enoate
  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.