(2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]-11'-(tert-butyldimethylsiloxy)dodecahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodec...) | 171625-80-2

• 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: (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]-11'-(tert-butyldimethylsiloxy)dodecahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodec...)
• 英文别名: (1'S,2'R,4S,4'S,5'S,7'R,9'S,11'S,12'S)-11'-[tert-butyl(dimethyl)silyl]oxy-12'-hydroxy-2'-(methoxymethoxy)-7'-[(4-methoxyphenyl)methoxy]-2,2,4',15',15'-pentamethyl-5'-(phenylmethoxymethoxy)spiro[1,3-dioxolane-4,8'-tricyclo[10.2.1.04,9]pentadecane]-3'-one
• CAS: 171625-80-2
• 化学式: C₄₆H₇₀O₁₁Si
• 分子量: 827.141
• InChiKey: BFLXQOWKLUFGRW-LWSMXPQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.21
• 重原子数：
  58.0
• 可旋转键数：
  14.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  120.37
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]-11'-(tert-butyldimethylsiloxy)dodecahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodec...) 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]dodecahydro-10'11'-dihydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodecen)-5'-one
  参考文献：
  名称：

  Selective Acylation Reactions of an Isotaxane Tetraol. A Direct Pathway to Introduction of the Oxetane Ring

  摘要：

  通过对四个可用的羟基取代基进行完全的化学控制，从四羟基 2 经过六个步骤合成了一种在环 C 和 D 中完全功能化为紫杉醇的异他烷。

  DOI：

  10.1055/s-1999-2911
• 作为产物：
  描述：

  苄基氯甲基醚 、 (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-11'-(tert-Butyldimethylsiloxy)dodecahydro-4',10'-dihydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodecen)-5'-one 在 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以86%的产率得到(2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]-11'-(tert-butyldimethylsiloxy)dodecahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(5'H)-[7,10]methanobenzocyclodec...)
  参考文献：
  名称：

  An Abbreviated, Highly Stereocontrolled Route to Precursors of Taxol. Elaboration of a Fully Functionalized C Ring by Means of Intramolecular Aldol Cyclization

  摘要：

  The asymmetric synthesis of an advanced taxol precursor is reported. The scheme involves the conversion of (R)-glyceraldehyde acetonide into the Q-vinyl iodide 2, transmetalation of this intermediate, and 1,2-addition to the D-camphor derivative 11 from the endo direction. This convergent coupling gives rise to exo alcohol 12, which undergoes anionic oxy-Cope rearrangement at low temperatures. In situ methylation of the resulting enolate anion delivers 13, which is chemoselectively transformed into aldehyde 18. In a key step, the aldol cyclization of 18 proceeds without beta-elimination to deliver a tricyclic product in which proper absolute configuration is adopted at the two stereogenic centers being newly introduced. Following protection of the hydroxyl substituent as in 19b,the alpha-hydroxy ketone 21 is heated with aluminum tri-tert-butoxide in benzene in order to effect near-quantitative rearrangement to the taxol-like isomer 22.

  DOI：

  10.1021/jo00129a027