Carbonic acid tert-butyl ester (Z)-(1R,2S)-1-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-2-methyl-hex-3-enyl ester | 1027306-01-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: Carbonic acid tert-butyl ester (Z)-(1R,2S)-1-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-2-methyl-hex-3-enyl ester
• 英文别名: tert-butyl [(Z,2R,3R,4S)-1-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethyloct-5-en-3-yl] carbonate
• CAS: 1027306-01-9
• 化学式: C₂₁H₄₂O₄Si
• 分子量: 386.648
• InChiKey: UZFJBPYAALGLBC-RXMKWERKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.57
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Carbonic acid tert-butyl ester (Z)-(1R,2S)-1-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-2-methyl-hex-3-enyl ester 在 一溴化碘 、 potassium carbonate 作用下， 生成 (2R,3S,4R)-1-(tert-Butyl-dimethyl-silanyloxy)-4-((2R,3S)-3-ethyl-oxiranyl)-2-methyl-pentan-3-ol
  参考文献：
  名称：

  Synthesis of a syn,syn,syn,syn-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A

  摘要：

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.

  DOI：

  10.1021/jo9902143
• 作为产物：
  描述：

  tert-butyl-[(2S)-hex-3-yn-2-yl]oxy-dimethylsilane 在 Lindlar's catalyst 正丁基锂 、 copper(I) bromide dimethylsulfide complex 、 三氟化硼乙醚 、 四丁基氟化铵 、 氢气 、 三正丁基氢锡 、 双(三甲基硅烷基)氨基钾 、 三乙胺 、 二异丙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 生成 Carbonic acid tert-butyl ester (Z)-(1R,2S)-1-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-2-methyl-hex-3-enyl ester
  参考文献：
  名称：

  Synthesis of a syn,syn,syn,syn-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A

  摘要：

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.

  DOI：

  10.1021/jo9902143

文献信息

• Synthesis of a <i>syn,syn,syn,syn</i>-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A
  作者：James A. Marshall、Russell N. Fitzgerald

  DOI：10.1021/jo9902143

  日期：1999.6.1

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.