(3aS,4S,5R,7aR)-7a-(tert-Butyl-dimethyl-silanyloxy)-5-hydroxy-4-hydroxymethyl-4-methyl-3a,4,5,7a-tetrahydro-3H-isobenzofuran-1-one | 144067-06-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异苯并呋喃
• 英文名称: (3aS,4S,5R,7aR)-7a-(tert-Butyl-dimethyl-silanyloxy)-5-hydroxy-4-hydroxymethyl-4-methyl-3a,4,5,7a-tetrahydro-3H-isobenzofuran-1-one
• 英文别名: (3aS,4S,5R,7aR)-7a-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4-(hydroxymethyl)-4-methyl-3a,5-dihydro-3H-2-benzofuran-1-one
• CAS: 144067-06-1
• 化学式: C₁₆H₂₈O₅Si
• 分子量: 328.481
• InChiKey: ZVLSECDRDPLWRA-CZPYZCIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.85
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aS,4S,5R,7aR)-7a-(tert-Butyl-dimethyl-silanyloxy)-5-hydroxy-4-hydroxymethyl-4-methyl-3a,4,5,7a-tetrahydro-3H-isobenzofuran-1-one 在 咪唑 、 lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 、 四丁基碘化铵 、 potassium hydride 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.0h， 生成 [(5S,6R,7R,8S)-8-Benzyloxy-7-(tert-butyl-diphenyl-silanyloxymethyl)-2,2,7-trimethyl-1,3-dioxa-spiro[4.5]dec-9-en-6-yl]-methanol
  参考文献：
  名称：

  Total Synthesis of Taxol. 3. Formation of Taxol's ABC Ring Skeleton

  摘要：

  The synthesis of Taxol's ABC ring system has been achieved. The Shapiro coupling of an aldehydic C ring synthon (8) with an anionic A ring synthon derived from hydrazone 9 gave, diastereoselectively, A-B conjugate 10. Functional group manipulations and McMurry ring closure produced the highly functionalized ABC ring system 17. Extensive attempts to optimize the McMurry reaction revealed a single predominant side reaction leading to byproducts 19 and 20. Resolution of the CB,C10-diol (+/-)-17 via its camphanyl esters provided the ABC ring system as its natural isomer (+)17.

  DOI：

  10.1021/ja00107a008
• 作为产物：
  描述：

  3-羟基-2-吡喃酮 在 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 、 2,2-二甲基-1,3-丙二醇 、 苯硼酸 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 51.83h， 生成 (3aS,4S,5R,7aR)-7a-(tert-Butyl-dimethyl-silanyloxy)-5-hydroxy-4-hydroxymethyl-4-methyl-3a,4,5,7a-tetrahydro-3H-isobenzofuran-1-one
  参考文献：
  名称：

  Synthesis of a fully functionalized CD ring system of taxol

  摘要：

  与紫杉醇 CD 环系统相关的关键构件 16 和 17 已通过立体控制的高效序列以外消旋形式合成，该序列具有新颖的 Diels-Alder 反应和氧杂环丁烷形成。

  DOI：

  10.1039/c39920001118

文献信息

• Enzymatic resolution of a key stereochemical intermediate for the synthesis of (−)-taxol
  作者：Carl R. Johnson、Yanping Xu、K.C. Nicolaou、Zhen Yang、Rodney K. Guy、Jian Guo Dong、Nina Berova

  DOI：10.1016/0040-4039(95)00523-f

  日期：1995.5

  The taxol intermediate, racemic 3, was subjected to two consecutive kinetic resolutions with recombinant Candida antarctica lipase Bin isopropenyl acetate/hexane. The absolute stereochemistry of the resulting acetate (+)-5 of > 99% enantiopurity, was assigned based on NMR and CD methods.
• Total Synthesis of taxol. 2. Construction of A and C ring intermediates and initial attempts to construct the ABC ring system
  作者：K. C. Nicolaou、J.-J. Liu、Z. Yang、H. Ueno、E. J. Sorensen、C. F. Claiborne、R. K. Guy、C.-K. Hwang、M. Nakada、P. G. Nantermet

  DOI：10.1021/ja00107a007

  日期：1995.1

  A method for the formation of Taxol's ABC ring system has been developed. General methods for the synthesis of versatile synthons for Taxol's A ring (8) and C ring (55) are presented. A model study using a simplified C ring synthon (17) confirmed the viability of the sequential Shapiro-McMurry strategy for formation of Taxol's B ring. Careful exploration of the chemistry of various A-B ring conjugates allowed the development of a successful method for formation of the B ring in a more functionalized system.