(2R,4R,5S,6S,7R)-9-(Benzyloxy)-4-(cyanomethyl)-5,7-(isopropylidenedioxy)-1-<<(p-methoxybenzyl)oxy>methoxy>-2,6-dimethylnonane | 138152-92-8

• 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: (2R,4R,5S,6S,7R)-9-(Benzyloxy)-4-(cyanomethyl)-5,7-(isopropylidenedioxy)-1-<<(p-methoxybenzyl)oxy>methoxy>-2,6-dimethylnonane
• CAS: 138152-92-8；138284-08-9
• 化学式: C₃₂H₄₅NO₆
• 分子量: 539.712
• InChiKey: IGTMRBWPSHSWBS-OTZOVASVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  39.0
• 可旋转键数：
  16.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  79.17
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (2R,4R,5S,6S,7R)-9-(Benzyloxy)-4-(cyanomethyl)-5,7-(isopropylidenedioxy)-1-<<(p-methoxybenzyl)oxy>methoxy>-2,6-dimethylnonane 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 (3R,5R)-3-[(4R,5R,6R)-6-(2-Benzyloxy-ethyl)-2,2,5-trimethyl-[1,3]dioxan-4-yl]-6-(4-methoxy-benzyloxymethoxy)-5-methyl-hexanal
  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：

  3-苄氧基丙醛 在 platinum(IV) oxide titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 草酰氯 、 18-冠醚-6 、 L-(+)-酒石酸二乙酯 、 3 A molecular sieve 、 lithium diethylamide 、 四丁基氟化铵 、 氢气 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 magnesium monoperoxyphthalate hexahydrate 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 异辛烷 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 97.84h， 生成 (2R,4R,5S,6S,7R)-9-(Benzyloxy)-4-(cyanomethyl)-5,7-(isopropylidenedioxy)-1-<<(p-methoxybenzyl)oxy>methoxy>-2,6-dimethylnonane
  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