(S)-2-((R)-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)((p-methoxybenzyl)oxy)methyl)glycidaldehyde diethyl acetal | 171625-77-7

• 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: (S)-2-((R)-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)((p-methoxybenzyl)oxy)methyl)glycidaldehyde diethyl acetal
• 英文别名: (4R)-4-[(R)-[(2S)-2-(diethoxymethyl)oxiran-2-yl]-[(4-methoxyphenyl)methoxy]methyl]-2,2-dimethyl-1,3-dioxolane
• CAS: 171625-77-7
• 化学式: C₂₁H₃₂O₇
• 分子量: 396.481
• InChiKey: LLSOAUHDJHGMPQ-OPYAIIAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  67.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (S)-2-((R)-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)((p-methoxybenzyl)oxy)methyl)glycidaldehyde diethyl acetal 在 吡啶 、 咪唑 、 sodium hydroxide 、 四氧化锇 、 sodium dithionite 、 18-冠醚-6 、 碘 、 叔丁基锂 、 sodium hexamethyldisilazane 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 三苯基膦 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 乙腈 为溶剂， 反应 22.28h， 生成 (1S,2R,4R,5S,7S,8S)-7-(tert-Butyl-dimethyl-silanyloxy)-8-hydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-2-methoxymethoxy-4,11,11-trimethyl-bicyclo[6.2.1]undecan-3-one
  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-desoxy-4,5-isopropylidene-2-C-methylene-D-pentose 在 叔丁基过氧化氢 、 vanadyl acetylacetonate 、 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 13.5h， 生成 (S)-2-((R)-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)((p-methoxybenzyl)oxy)methyl)glycidaldehyde diethyl acetal
  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

文献信息

• An Abbreviated, Highly Stereocontrolled Route to Precursors of Taxol. Elaboration of a Fully Functionalized C Ring by Means of Intramolecular Aldol Cyclization
  作者：Leo A. Paquette、Francis J. Montgomery、Ting-Zhong Wang

  DOI：10.1021/jo00129a027

  日期：1995.12

  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.