2-((E)-4-Bromo-3-methyl-but-2-enyl)-5-{(E)-2-methyl-3-[5-oxo-4-(2-oxo-ethyl)-2,5-dihydro-furan-2-yl]-propenyl}-furan-3-carboxylic acid methyl ester | 145474-29-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-((E)-4-Bromo-3-methyl-but-2-enyl)-5-{(E)-2-methyl-3-[5-oxo-4-(2-oxo-ethyl)-2,5-dihydro-furan-2-yl]-propenyl}-furan-3-carboxylic acid methyl ester
• 英文别名: methyl 2-[(E)-4-bromo-3-methylbut-2-enyl]-5-[(E)-2-methyl-3-[5-oxo-4-(2-oxoethyl)-2H-furan-2-yl]prop-1-enyl]furan-3-carboxylate
• CAS: 145474-29-9
• 化学式: C₂₁H₂₃BrO₆
• 分子量: 451.314
• InChiKey: HCYWHYJVDFNHQA-ZFTQYTBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  82.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-((E)-4-Bromo-3-methyl-but-2-enyl)-5-{(E)-2-methyl-3-[5-oxo-4-(2-oxo-ethyl)-2,5-dihydro-furan-2-yl]-propenyl}-furan-3-carboxylic acid methyl ester 在 lithium aluminium tetrahydride 、 三氯化铬 作用下， 以 四氢呋喃 为溶剂， 以20%的产率得到(E)-(5R,10S,11R)-10-Hydroxy-11-isopropenyl-3-methyl-7-oxo-6,16-dioxa-tricyclo[11.2.1.1^5,8]heptadeca-1(15),2,8(17),13-tetraene-14-carboxylic acid methyl ester
  参考文献：
  名称：

  Total synthesis of furanocembranolides. 3. A concise convergent route to acerosolide

  摘要：

  The first synthesis of a 14-membered furanocembranolide has been achieved. The target molecule, acerosolide, contains two stereogenic cetners whose relative and absolute configuration have not previously been assigned. MM2 calculations performed during the course of the present work suggest their configuration to be 1(S*),10(R*). The synthesis began by SnCl2-promoted condensation of allylstannane 6 to aldehyde 7 so as to achieve regioreversed condensation and formation of the extended allylic alcohol 9. Acid-catalyzed lactonization and 2-fold oxidation via the bis-selenide gave butenolide 11 and subsequently the derived bromide 12b. Palladium(0)-catalyzed condensation of 12b with vinylstannane 13 provided seco-cembrane 14. Following the elaboration of 14 into bromo aldehyde 16, macrocyclization was effected with chromous chloride. The single homoallylic alcohol produced by this means underwent oxidation to give acerosolide, as deduced by proper spectral comparison with the natural product.

  DOI：

  10.1021/jo00053a031
• 作为产物：
  描述：

  5-[(E)-6-tert-Butoxycarbonyl-8-(tert-butyl-diphenyl-silanyloxy)-4-hydroxy-2-methyl-oct-1-enyl]-2-phenylsulfanylmethyl-furan-3-carboxylic acid methyl ester 在 四(三苯基膦)钯 sodium tetrahydroborate 、 sodium periodate 、 N-溴代丁二酰亚胺(NBS) 、 重铬酸吡啶 、 二甲基硫 、 (Me₂Si)2NK 、 D(+)-10-樟脑磺酸 、 氢氟酸 、 溴 、 silver perchlorate 、 碳酸氢钠 、 1,2-双(二苯基膦)乙烷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 水 、 乙腈 、 苯 为溶剂， 反应 70.0h， 生成 2-((E)-4-Bromo-3-methyl-but-2-enyl)-5-{(E)-2-methyl-3-[5-oxo-4-(2-oxo-ethyl)-2,5-dihydro-furan-2-yl]-propenyl}-furan-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Total synthesis of furanocembranolides. 3. A concise convergent route to acerosolide

  摘要：

  The first synthesis of a 14-membered furanocembranolide has been achieved. The target molecule, acerosolide, contains two stereogenic cetners whose relative and absolute configuration have not previously been assigned. MM2 calculations performed during the course of the present work suggest their configuration to be 1(S*),10(R*). The synthesis began by SnCl2-promoted condensation of allylstannane 6 to aldehyde 7 so as to achieve regioreversed condensation and formation of the extended allylic alcohol 9. Acid-catalyzed lactonization and 2-fold oxidation via the bis-selenide gave butenolide 11 and subsequently the derived bromide 12b. Palladium(0)-catalyzed condensation of 12b with vinylstannane 13 provided seco-cembrane 14. Following the elaboration of 14 into bromo aldehyde 16, macrocyclization was effected with chromous chloride. The single homoallylic alcohol produced by this means underwent oxidation to give acerosolide, as deduced by proper spectral comparison with the natural product.

  DOI：

  10.1021/jo00053a031