tert-butyl-[(5R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methoxy]hex-2-ynoxy]-dimethylsilane | 397851-60-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl-[(5R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methoxy]hex-2-ynoxy]-dimethylsilane
• CAS: 397851-60-4
• 化学式: C₂₆H₄₆O₄Si₂
• 分子量: 478.82
• InChiKey: ZOAOOMUDSOTIAH-XMMPIXPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.02
• 重原子数：
  32
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl-[(5R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methoxy]hex-2-ynoxy]-dimethylsilane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 23.0h， 以6.42 g的产率得到(2R)-2-(tert-butyldimethylsilanyloxy)-1-(4'-methoxybenzyloxy)hex-4-yn-6-ol
  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：

  (2R)-6-[tert-butyl(dimethyl)silyl]oxy-1-[(4-methoxyphenyl)methoxy]hex-4-yn-2-ol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 40.0h， 生成 tert-butyl-[(5R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methoxy]hex-2-ynoxy]-dimethylsilane
  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.