(2S,3S,5R)-7-(Benzyloxy)-2-ethyl-4-methylene-1-<(tert-butyldimethylsilyl)oxy>heptane-3,5-diol | 138152-71-3

• 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: (2S,3S,5R)-7-(Benzyloxy)-2-ethyl-4-methylene-1-<(tert-butyldimethylsilyl)oxy>heptane-3,5-diol
• 英文别名: (3R,5S,6S)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-methylidene-1-phenylmethoxyoctane-3,5-diol
• CAS: 138152-71-3
• 化学式: C₂₃H₄₀O₄Si
• 分子量: 408.654
• InChiKey: BEYZYRQXIMDKDL-BHDDXSALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  28
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3S,5R)-7-(Benzyloxy)-2-ethyl-4-methylene-1-<(tert-butyldimethylsilyl)oxy>heptane-3,5-diol 在 platinum(IV) oxide 氢气 、 4-甲基苯磺酸吡啶 作用下， 以 乙醇 为溶剂， 反应 36.25h， 生成 (2S,3S,4S,5R)-7-(Benzyloxy)-2-ethyl-4-methyl-1-<(tert-butyldimethylsilyl)oxy>-3,5-(isopropylidenedioxy)heptane
  参考文献：
  名称：

  SN2' addition of cuprates to acyclic vinyloxiranes. Synthesis of tylactone and tylonolide subunits

  摘要：

  The chiral acyclic vinyloxiranes 8 and 18 undergo highly anti selective S(N)2' additions upon treatment with Et2CuLi and (S)-PMBOMOCH2CH(CH3)CH2Cu(CN)Li, respectively. The product of the former addition, diol 9, affords the alpha-epoxide 12 upon epoxidation with m-CPBA. Conversion to acetonide 15, a possible C-1-C-7 segment of tylactone, was effected by hydrogenation of the methylene acetonide 14 obtained from epoxide 12 through LiNEt2 elimination and ketalization with 2,2-dimethoxypropane (2,2-DMP). Allylic alcohol 24b, a close analogue of diol 9, gave only the beta-epoxide 25b upon treatment with m-CPBA. Epoxidation with magnesium monoperoxyphthalic acid (MMPP), however, yielded a separable 53:47 mixture of beta- and alpha-epoxides 25b and 26b. The former was carried on to acetonide 29 by a sequence involving basic elimination (LiNEt2), treatment with 2,2-DMP, and hydrogenation. Acetonide 30, a diastereomer of 29, was prepared from epoxide 26b by a parallel sequence. Acetonide 30 was converted to the lactol methyl ether 48, an intermediate in Nicolaou's synthesis of O-micinosyl tylonolide, through displacement of tosylate 43 with KCN and then reduction (DIBAH), methanolysis (HCl, MeOH), silylation (TBSOTf, 2,6-lutidine), and finally PMBOM cleavage (DDQ). An identical sequence was applied to acetonide 29 resulting in the isomeric lactol methyl ether 37.

  DOI：

  10.1021/jo00027a022
• 作为产物：
  描述：

  (3R,4S,5S,6R)-1-(Benzyloxy)-4,5-epoxy-6-ethyl-4-methyl-7-<(tert-butyldimethylsilyl)oxy>-4-heptanol 在 lithium diethylamide 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 72.0h， 以73%的产率得到(2S,3S,5R)-7-(Benzyloxy)-2-ethyl-4-methylene-1-<(tert-butyldimethylsilyl)oxy>heptane-3,5-diol
  参考文献：
  名称：

  SN2' addition of cuprates to acyclic vinyloxiranes. Synthesis of tylactone and tylonolide subunits

  摘要：

  The chiral acyclic vinyloxiranes 8 and 18 undergo highly anti selective S(N)2' additions upon treatment with Et2CuLi and (S)-PMBOMOCH2CH(CH3)CH2Cu(CN)Li, respectively. The product of the former addition, diol 9, affords the alpha-epoxide 12 upon epoxidation with m-CPBA. Conversion to acetonide 15, a possible C-1-C-7 segment of tylactone, was effected by hydrogenation of the methylene acetonide 14 obtained from epoxide 12 through LiNEt2 elimination and ketalization with 2,2-dimethoxypropane (2,2-DMP). Allylic alcohol 24b, a close analogue of diol 9, gave only the beta-epoxide 25b upon treatment with m-CPBA. Epoxidation with magnesium monoperoxyphthalic acid (MMPP), however, yielded a separable 53:47 mixture of beta- and alpha-epoxides 25b and 26b. The former was carried on to acetonide 29 by a sequence involving basic elimination (LiNEt2), treatment with 2,2-DMP, and hydrogenation. Acetonide 30, a diastereomer of 29, was prepared from epoxide 26b by a parallel sequence. Acetonide 30 was converted to the lactol methyl ether 48, an intermediate in Nicolaou's synthesis of O-micinosyl tylonolide, through displacement of tosylate 43 with KCN and then reduction (DIBAH), methanolysis (HCl, MeOH), silylation (TBSOTf, 2,6-lutidine), and finally PMBOM cleavage (DDQ). An identical sequence was applied to acetonide 29 resulting in the isomeric lactol methyl ether 37.

  DOI：

  10.1021/jo00027a022