cis-8a-(2-Hexynyl)octahydro-1H-cycloheptafuran-1-one | 130082-83-6

• 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: cis-8a-(2-Hexynyl)octahydro-1H-cycloheptafuran-1-one
• 英文别名: (3aR,8aR)-3a-hex-2-ynyl-4,5,6,7,8,8a-hexahydro-1H-cyclohepta[c]furan-3-one
• CAS: 130082-83-6
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: DEXXVRHYKSDXKO-ZFWWWQNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-8a-(2-Hexynyl)octahydro-1H-cycloheptafuran-1-one 在 吡啶 、 lithium aluminium tetrahydride 、 二甲基硫 、 三乙基硼 、 sodium hydride 、 三乙基硼氢化锂 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 96.92h， 生成 trans-Octahydro-3a-methyl-2(1H)-azulenone
  参考文献：
  名称：

  Formation of trans ring-fused compounds by an alkylation-radical cyclization sequence

  摘要：

  Enolates derived from bicyclic lactones of type 1 (Scheme I) can be alkylated with 2-propynylic halides to give products 2, in which the unsaturated alkyl group is syn to the adjacent ring-fusion hydrogen. Reaction of 2 with sodium phenyl selenide and then with diazomethane produces esters 3, and these give trans ring-fused bicyclic compounds 4 when treated with triphenyltin hydride in the presence of a radical initiator. The bicyclic compounds afford ketones on double-bond cleavage, and the angular ester function can be converted into a methyl group. Similar processes occur if an aldehyde is used in the first step instead of a halide. The methodology is general.

  DOI：

  10.1021/jo00076a057
• 作为产物：
  描述：

  cis/trans-Hexahydro-1H-cycloheptafuran-1,3-dione 在 sodium tetrahydroborate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.67h， 生成 cis-8a-(2-Hexynyl)octahydro-1H-cycloheptafuran-1-one
  参考文献：
  名称：

  Formation of trans ring-fused compounds by an alkylation-radical cyclization sequence

  摘要：

  Enolates derived from bicyclic lactones of type 1 (Scheme I) can be alkylated with 2-propynylic halides to give products 2, in which the unsaturated alkyl group is syn to the adjacent ring-fusion hydrogen. Reaction of 2 with sodium phenyl selenide and then with diazomethane produces esters 3, and these give trans ring-fused bicyclic compounds 4 when treated with triphenyltin hydride in the presence of a radical initiator. The bicyclic compounds afford ketones on double-bond cleavage, and the angular ester function can be converted into a methyl group. Similar processes occur if an aldehyde is used in the first step instead of a halide. The methodology is general.

  DOI：

  10.1021/jo00076a057

文献信息

• Construction of trans-ring-fused compounds by radical cyclızation
  作者：Derrick L. J. Clive、Hartford W. Manning、Taryn L. B. Boivin

  DOI：10.1039/c39900000972

  日期：——

  hydrogen; prop-2-ynylic aldehydes can be used instead of halides and, in both cases, lactone opening with sodium phenyl selenide, esterification, and treatment with a stannane then leads to trans-ring-fused bicyclic compounds.

  用丙-2-炔（和烯丙基）溴化物将衍生自（4）型双环内酯的烯醇化物烷基化，得到产物（5），其中不饱和烷基与剩余的环稠合氢同构；丙-2- ynylic醛类可以被用来代替卤化物，并且在这两种情况下，内酯开与苯基硒化钠，酯化和治疗与锡烷然后导致反形环稠合的双环化合物。
• Formation of trans ring-fused compounds by an alkylation-radical cyclization sequence
  作者：Derrick L. J. Clive、Hartford W. Manning、Taryn L. B. Boivin、Maarten H. D. Postema

  DOI：10.1021/jo00076a057

  日期：1993.11

  Enolates derived from bicyclic lactones of type 1 (Scheme I) can be alkylated with 2-propynylic halides to give products 2, in which the unsaturated alkyl group is syn to the adjacent ring-fusion hydrogen. Reaction of 2 with sodium phenyl selenide and then with diazomethane produces esters 3, and these give trans ring-fused bicyclic compounds 4 when treated with triphenyltin hydride in the presence of a radical initiator. The bicyclic compounds afford ketones on double-bond cleavage, and the angular ester function can be converted into a methyl group. Similar processes occur if an aldehyde is used in the first step instead of a halide. The methodology is general.