2-desoxy-4,5-isopropylidene-2-C-methylene-D-pentose | 69309-97-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-desoxy-4,5-isopropylidene-2-C-methylene-D-pentose
• CAS: 69309-97-3；69309-98-4；102629-15-2
• 化学式: C₁₃H₂₄O₅
• 分子量: 260.331
• InChiKey: PGARUTMSQDPWSS-NFJWQWPMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.45
• 重原子数：
  18.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-desoxy-4,5-isopropylidene-2-C-methylene-D-pentose 在 咪唑 、 叔丁基过氧化氢 、 sodium hydroxide 、 vanadyl acetylacetonate 、 碘 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 三苯基膦 作用下， 以 乙醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 31.0h， 生成 (5S,8S,9R)-6-Ethoxy-8-(iodomethyl)-9-<(p-methoxybenzyl)oxy>-2,2-dimethyl-1,3,7-trioxaspiro<4.4>nonane
  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-溴丙烯醛二乙缩醛 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以90%的产率得到2-desoxy-4,5-isopropylidene-2-C-methylene-D-pentose
  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

• Synthesis of 1,1-Diethoxy-2-methylene-3-oxoalkanes(α-Methylene-β-oxoacetals)
  作者：J. C. Depezay、Y. Le Merrer、M. Saniere

  DOI：10.1055/s-1985-31340

  日期：——
• Synthèse de dérivés de pentos-3-uloses branchés sur le carbone 2. Epoxydation chimique et enzymatique de l'acétal diéthylique du 2-désoxy-4,5-O- isopropylidène-2-C-méthylène-d-glycéro-pentos-3-ulose
  作者：Jean-Claude Depezay、Michèle Sanière、Daniel Mansuy

  DOI：10.1016/0008-6215(83)88100-2

  日期：1983.6