(4S,5R,6R)-4-[(R)-2-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-6-((R)-1-iodo-propyl)-5-methyl-[1,3]dioxan-2-one | 236390-82-2

• 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: (4S,5R,6R)-4-[(R)-2-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-6-((R)-1-iodo-propyl)-5-methyl-[1,3]dioxan-2-one
• 英文别名: (4S,5R,6R)-4-[(2R)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]-6-[(1R)-1-iodopropyl]-5-methyl-1,3-dioxan-2-one
• CAS: 236390-82-2
• 化学式: C₁₇H₃₃IO₄Si
• 分子量: 456.437
• InChiKey: CDCVWEYIFFOFIP-ARILJUKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 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：

  (4S,5R,6R)-4-[(R)-2-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-6-((R)-1-iodo-propyl)-5-methyl-[1,3]dioxan-2-one 在 potassium carbonate 作用下， 以77%的产率得到(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：

  (Z)-(2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-oct-5-en-3-ol 在 一溴化碘 、 双(三甲基硅烷基)氨基钾 作用下， 生成 (4S,5R,6R)-4-[(R)-2-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-6-((R)-1-iodo-propyl)-5-methyl-[1,3]dioxan-2-one
  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