(E)-5-[(4S,5R)-5-[(2R,4S,5S,6R)-6-[(E)-3-[(1R,3S,4R,5R,7R)-7-[(E)-2-iodoethenyl]-4-methyl-2,6-dioxabicyclo[3.2.1]octan-3-yl]prop-2-enyl]-4-(methoxymethoxy)-5-methyloxan-2-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]pent-4-enal | 1186073-85-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-5-[(4S,5R)-5-[(2R,4S,5S,6R)-6-[(E)-3-[(1R,3S,4R,5R,7R)-7-[(E)-2-iodoethenyl]-4-methyl-2,6-dioxabicyclo[3.2.1]octan-3-yl]prop-2-enyl]-4-(methoxymethoxy)-5-methyloxan-2-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]pent-4-enal
• CAS: 1186073-85-7
• 化学式: C₃₀H₄₅IO₈
• 分子量: 660.587
• InChiKey: PNZWZCSSEZTEMG-YTJAKKAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (E)-5-[(4S,5R)-5-[(2R,4S,5S,6R)-6-[(E)-3-[(1R,3S,4R,5R,7R)-7-[(E)-2-iodoethenyl]-4-methyl-2,6-dioxabicyclo[3.2.1]octan-3-yl]prop-2-enyl]-4-(methoxymethoxy)-5-methyloxan-2-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]pent-4-enal 、 tert-butyl (E,6R)-8-[(2S,3S,6S)-3-[tert-butyl(dimethyl)silyl]oxy-6-[2-(1-phenyltetrazol-5-yl)sulfonylethyl]-3,6-dihydro-2H-pyran-2-yl]-6-methylnon-7-enoate 在 双(三甲基硅烷基)氨基钾 作用下， 以 乙二醇二甲醚 、 甲苯 为溶剂， 反应 2.25h， 以79%的产率得到tert-butyl (E,6R)-8-[(2S,3S,6S)-3-[tert-butyl(dimethyl)silyl]oxy-6-[(2E,6E)-7-[(4S,5R)-5-[(2R,4S,5S,6R)-6-[(E)-3-[(1R,3S,4R,5R,7R)-7-[(E)-2-iodoethenyl]-4-methyl-2,6-dioxabicyclo[3.2.1]octan-3-yl]prop-2-enyl]-4-(methoxymethoxy)-5-methyloxan-2-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]hepta-2,6-dienyl]-3,6-dihydro-2H-pyran-2-yl]-6-methylnon-7-enoate
  参考文献：
  名称：

  Formal Synthesis of (+)-Sorangicin A

  摘要：

  The formal synthesis of (+)-sorangicin A was completed by two independent routes. Both approaches feature a cross metathesis reaction to form the C29-C30 bond to arrive at the bicyclic ether/tetrahydropyran fragment. Formation of the C15-C16 olefin to unite the dihydropyran fragment with the rest of the molecule was achieved by either a cross metathesis reaction or a Julia-Kocienski olefination.

  DOI：

  10.1021/ol201920j
• 作为产物：
  描述：

  在 chromium dichloride 、 四丁基氟化铵 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 (E)-5-[(4S,5R)-5-[(2R,4S,5S,6R)-6-[(E)-3-[(1R,3S,4R,5R,7R)-7-[(E)-2-iodoethenyl]-4-methyl-2,6-dioxabicyclo[3.2.1]octan-3-yl]prop-2-enyl]-4-(methoxymethoxy)-5-methyloxan-2-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]pent-4-enal
  参考文献：
  名称：

  Formal Synthesis of (+)-Sorangicin A

  摘要：

  The formal synthesis of (+)-sorangicin A was completed by two independent routes. Both approaches feature a cross metathesis reaction to form the C29-C30 bond to arrive at the bicyclic ether/tetrahydropyran fragment. Formation of the C15-C16 olefin to unite the dihydropyran fragment with the rest of the molecule was achieved by either a cross metathesis reaction or a Julia-Kocienski olefination.

  DOI：

  10.1021/ol201920j

文献信息

• Total Synthesis of (+)-Sorangicin A
  作者：Amos B. Smith、Shuzhi Dong、Jehrod B. Brenneman、Richard J. Fox

  DOI：10.1021/ja906115a

  日期：2009.9.2

  The final synthetic challenges associated with (+)-sorangicin A have been overcome, thus leading to the first total synthesis of this complex macrolide antibiotic. Highlights of the highly convergent synthesis include two Julia-Kocienski olefinations to unite three advanced fragments with high E-stereoselectivity. Critical to the final-stage success was the use of a carefully defined Stille coupling and a Mukaiyama macrolactonization as well as Lewis and protic acid-promoted deprotections carefully designed to suppress E/Z isomerization and/or destruction of the delicate (Z,Z,E)-trienoate linkage.