(2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]octahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(2'H)-[7,10]methanobenzocyclodecene)-5',11'(3'H,6'H)-dione | 171625-75-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]octahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(2'H)-[7,10]methanobenzocyclodecene)-5',11'(3'H,6'H)-dione
• 英文别名: (1'S,4S,4'S,6'R,8'S,9'S,11'R,12'S)-1'-hydroxy-11'-(methoxymethoxy)-6'-[(4-methoxyphenyl)methoxy]-2,2,9',15',15'-pentamethyl-8'-(phenylmethoxymethoxy)spiro[1,3-dioxolane-4,5'-tricyclo[10.2.1.04,9]pentadecane]-2',10'-dione
• CAS: 171625-75-5
• 化学式: C₄₀H₅₄O₁₁
• 分子量: 710.862
• InChiKey: MWFJSSPLIMAZGJ-WHDIPZTKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  51
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  128
• 氢给体数：
  1
• 氢受体数：
  11

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]octahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(2'H)-[7,10]methanobenzocyclodecene)-5',11'(3'H,6'H)-dione 在 aluminum tri-tert-butoxide 作用下， 以 苯 为溶剂， 反应 12.0h， 以94%的产率得到(1'S,3R,4S,4'aS,6'R,10'S,12'aS)-1'-[(Benzyloxy)methoxy]decahydro-6'-hydroxy-3'-[(p-methoxybenzyl)oxy]-11'-(methoxymethoxy)-2,2,12'a,13',13'-pentamethylspiro(1,3-dioxolane-4,4'(1'H)-[6,10]methanobenzocyclodecene)-7',12'-dione
  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
• 作为产物：
  描述：

  (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 在 草酰氯 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 生成 (2'R,4S,4'S,4'aS,6'R,7'S,10'S,11'S,12'aS)-4'-[(Benzyloxy)methoxy]octahydro-10'-hydroxy-2'-[(p-methoxybenzyl)oxy]-6'-(methoxymethoxy)-2,2,4'a,13',13'-pentamethylspiro(1,3-dioxolane-4,1'(2'H)-[7,10]methanobenzocyclodecene)-5',11'(3'H,6'H)-dione
  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