(8R)-8-[(1R,2R)-2-(tert-butyldiphenylsilanyloxymethyl)cyclopropyl]-octahydrooxocin-2-one | 1029316-88-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (8R)-8-[(1R,2R)-2-(tert-butyldiphenylsilanyloxymethyl)cyclopropyl]-octahydrooxocin-2-one
• 英文别名: (8R)-8-[(1R,2R)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]cyclopropyl]oxocan-2-one
• CAS: 1029316-88-8
• 化学式: C₂₇H₃₆O₃Si
• 分子量: 436.667
• InChiKey: XQGPOVWUXMWHSY-FTBPSBKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  (8R)-8-[(1R,2R)-2-(tert-butyldiphenylsilanyloxymethyl)cyclopropyl]-octahydrooxocin-2-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以99%的产率得到(8R)-8-[(1R,2R)-2-(hydroxymethyl)cyclopropyl]octahydrooxocin-2-one
  参考文献：
  名称：

  Solandelactones A，B，E和F的全合成开发了串联Petasis-Claisen酸化策略

  摘要：

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.

  DOI：

  10.1021/jo800335g
• 作为产物：
  描述：

  (8R)-8-[(1R,2R)-2-(tert-butyldiphenylsilanyloxymethyl)cyclopropyl]-3,4,7,8-tetrahydrooxocin-2-one 在 吡啶 、 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 13.0h， 以73%的产率得到(8R)-8-[(1R,2R)-2-(tert-butyldiphenylsilanyloxymethyl)cyclopropyl]-octahydrooxocin-2-one
  参考文献：
  名称：

  Solandelactones A，B，E和F的全合成开发了串联Petasis-Claisen酸化策略

  摘要：

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.

  DOI：

  10.1021/jo800335g

文献信息

• Total Synthesis of Solandelactones A, B, E, and F Exploiting a Tandem Petasis−Claisen Lactonization Strategy
  作者：James D. White、Christopher M. Lincoln、Jongtae Yang、William H. C. Martin、David B. Chan

  DOI：10.1021/jo800335g

  日期：2008.6.1

  Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyania-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C(22) oxylipins that parallels a hypothesis put forward previously to explain the origin of C(20) cyclopropane-containing algal products.