(+/-)-2-(2',3'-di[(tert-butyldimethylsilyl)oxy]-4'-methoxyphenyl)-2-(3,4,5-trimethoxyphenyl)acetaldehyde | 309947-17-9

• 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-(2',3'-di[(tert-butyldimethylsilyl)oxy]-4'-methoxyphenyl)-2-(3,4,5-trimethoxyphenyl)acetaldehyde
• 英文别名: 2-[2,3-Bis[[tert-butyl(dimethyl)silyl]oxy]-4-methoxyphenyl]-2-(3,4,5-trimethoxyphenyl)acetaldehyde
• CAS: 309947-17-9
• 化学式: C₃₀H₄₈O₇Si₂
• 分子量: 576.878
• InChiKey: QRZMWUJUDIGCEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.82
• 重原子数：
  39
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (+/-)-2-(2',3'-di[(tert-butyldimethylsilyl)oxy]-4'-methoxyphenyl)-2-(3,4,5-trimethoxyphenyl)acetaldehyde 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以49%的产率得到hydroxyphenstatin
  参考文献：
  名称：

  A Pinacol Rearrangement/Oxidation Synthetic Route to Hydroxyphenstatin¹

  摘要：

  In an attempt to develop biologically active compounds from the inactive trans isomer (3a) of stilbene la, after asymmetric dihydroxylation to optically pure (R,R)-diol 8 the unexpected racemic diphenylacetaldehyde (9) was generated via a Pinacol rearrangement. Several derivatives of diphenylacetaldehyde 9 were synthesized (11-15) and reported. Further reaction of aldehyde 9 during desilylation through autoxidative decarbonylation afforded benzophenone 2b, designated hydroxyphenstatin, a potent antitumor and antimitotic agent. Hydroxyphenstatin showed potent inhibition of the tubulin assembly (IC50 0.82 muM) and exhibited an ED50 of 2.5 mug/mL against the P388 lymphocytic leukemia cell line.

  DOI：

  10.1021/jo000705j
• 作为产物：
  描述：

  1-[2,3-bis[[tert-butyl(dimethyl)silyl]oxy]-4-methoxyphenyl]-2-(3,4,5-trimethoxyphenyl)ethane-1,2-diol 在 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以72%的产率得到(+/-)-2-(2',3'-di[(tert-butyldimethylsilyl)oxy]-4'-methoxyphenyl)-2-(3,4,5-trimethoxyphenyl)acetaldehyde
  参考文献：
  名称：

  芳香醛的无金属和无O 2氧化性C–C键裂解

  摘要：

  发现不需要金属或O 2的醛的氧化C–C裂解。使用亚硝基苯作为氧化剂，将高苄基醛和α-取代的高苄基醛分别裂解为苄基醛和酮。该反应对芳族醛是化学选择性的，因为脂族醛在这些条件下是不反应的，并且可以耐受其他反应性官能团，例如酮和游离醇。提出了一种机制来解释碳损失的命运。

  DOI：

  10.1021/acs.joc.7b00784

文献信息

• Metal- and O₂-Free Oxidative C–C Bond Cleavage of Aromatic Aldehydes
  作者：Guang Hu、Kinthada Ramakumar、Stacey E. Brenner-Moyer

  DOI：10.1021/acs.joc.7b00784

  日期：2017.7.7

  An oxidative C–C cleavage of aldehydes requiring neither metals nor O2 was discovered. Homobenzylic aldehydes and α-substituted homobenzylic aldehydes were cleaved to benzylic aldehydes and ketones, respectively, using nitrosobenzene as an oxidant. This reaction is chemoselective for aromatic aldehydes, as an aliphatic aldehyde was unreactive under these conditions, and other reactive functionality

  发现不需要金属或O 2的醛的氧化C–C裂解。使用亚硝基苯作为氧化剂，将高苄基醛和α-取代的高苄基醛分别裂解为苄基醛和酮。该反应对芳族醛是化学选择性的，因为脂族醛在这些条件下是不反应的，并且可以耐受其他反应性官能团，例如酮和游离醇。提出了一种机制来解释碳损失的命运。
• A Pinacol Rearrangement/Oxidation Synthetic Route to Hydroxyphenstatin¹
  作者：George R. Pettit、John W. Lippert、Delbert L. Herald

  DOI：10.1021/jo000705j

  日期：2000.11.1

  In an attempt to develop biologically active compounds from the inactive trans isomer (3a) of stilbene la, after asymmetric dihydroxylation to optically pure (R,R)-diol 8 the unexpected racemic diphenylacetaldehyde (9) was generated via a Pinacol rearrangement. Several derivatives of diphenylacetaldehyde 9 were synthesized (11-15) and reported. Further reaction of aldehyde 9 during desilylation through autoxidative decarbonylation afforded benzophenone 2b, designated hydroxyphenstatin, a potent antitumor and antimitotic agent. Hydroxyphenstatin showed potent inhibition of the tubulin assembly (IC50 0.82 muM) and exhibited an ED50 of 2.5 mug/mL against the P388 lymphocytic leukemia cell line.