(2R)-1-O-(tert-butyldiphenylsilyl)-2-[(1S)-1,2-bis(benzyloxy)ethyl]-4-pentene-1,2-diol | 153096-85-6

• 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: (2R)-1-O-(tert-butyldiphenylsilyl)-2-[(1S)-1,2-bis(benzyloxy)ethyl]-4-pentene-1,2-diol
• CAS: 153096-85-6
• 化学式: C₃₇H₄₄O₄Si
• 分子量: 580.839
• InChiKey: FFVLMNHXAWNXGH-YBZKQSBQSA-N

物化性质

• 沸点：
  645.8±55.0 °C(predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.67
• 重原子数：
  42.0
• 可旋转键数：
  15.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2R)-1-O-(tert-butyldiphenylsilyl)-2-[(1S)-1,2-bis(benzyloxy)ethyl]-4-pentene-1,2-diol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以90%的产率得到(2R)-2-[(1S)-1,2-bis(benzyloxy)ethyl]-4-pentene-1,2-diol
  参考文献：
  名称：

  Stereoselective allylations of erythrulose derivatives under anhydrous conditions

  摘要：

  We have investigated a number of nucleophilic additions or allylating reagents to several alpha,alpha ',beta -trioxygenated ketones (O-protected erythrulose derivatives), Reagents based on lithium. magnesium. copper and titanium stereoselectivities and did not display any recognizable trend in the sense of stereoselection. In contrast, reactions involving silicon and tin derivatives were highly stereoselective and gage rise to essentially a single diastereoisomer, the structure of which depended group. Thus, alpha,beta -di-O-benzylated derivatives experienced almost exclusive addition to the carbonyl Si on the type or protecting group side, whereas alpha,beta -O,O-alkylidene derivatives (dioxolane acetals) yielded the opposite diastereoisomers as a result of addition to the Re side. These results Suggest the intermediacy of a-chelates in the additions or silicon and tin reagents to the di-O-benzylated derivatives. In contrast, the opposite stereoisomers. formed in the reactions of dioxolanes. are believed to be formed through Felkin-Anh transition states, pointing to the reluctance of acetal ox gens to participate in chelated intermediates. (C) 2001 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(01)00262-2
• 作为产物：
  描述：

  烯丙基三丁基锡 、 (S)-3,4-Bis-benzyloxy-1-(tert-butyl-diphenyl-silanyloxy)-butan-2-one 在 4 A molecular sieve 、 magnesium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以80%的产率得到(2R)-1-O-(tert-butyldiphenylsilyl)-2-[(1S)-1,2-bis(benzyloxy)ethyl]-4-pentene-1,2-diol
  参考文献：
  名称：

  Stereoselective allylations of erythrulose derivatives under anhydrous conditions

  摘要：

  We have investigated a number of nucleophilic additions or allylating reagents to several alpha,alpha ',beta -trioxygenated ketones (O-protected erythrulose derivatives), Reagents based on lithium. magnesium. copper and titanium stereoselectivities and did not display any recognizable trend in the sense of stereoselection. In contrast, reactions involving silicon and tin derivatives were highly stereoselective and gage rise to essentially a single diastereoisomer, the structure of which depended group. Thus, alpha,beta -di-O-benzylated derivatives experienced almost exclusive addition to the carbonyl Si on the type or protecting group side, whereas alpha,beta -O,O-alkylidene derivatives (dioxolane acetals) yielded the opposite diastereoisomers as a result of addition to the Re side. These results Suggest the intermediacy of a-chelates in the additions or silicon and tin reagents to the di-O-benzylated derivatives. In contrast, the opposite stereoisomers. formed in the reactions of dioxolanes. are believed to be formed through Felkin-Anh transition states, pointing to the reluctance of acetal ox gens to participate in chelated intermediates. (C) 2001 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(01)00262-2

文献信息

• Diastereoselectivity in Organometallic Additions to the Carbonyl Group of Protected Erythrulose Derivatives
  作者：J. Alberto Marco、Miguel Carda、Florenci González、Santiago Rodríguez、Encarna Castillo、Juan Murga

  DOI：10.1021/jo9716744

  日期：1998.2.1

  We have investigated a number of nucleophillic additions to L-erythrulose derivatives (4-12) bearing protective O-silyl, O-benzyl, and O-trityl groups in various relative positions. The results are discussed in the frame of chelated vs nonchelated transition states with additional support of previously published theoretical calculations. Sound evidence appears to exist for the formation of alpha-chelates as the key intermediates in nucleophillic additions to these alpha,beta-dioxygenated ketones. Since such evidence is still lacking in the case of beta-chelates, proposals of their intermediacy have been relegated in favor of the more solid Felkin-Anh model, which predicts the same stereochemical result. The behavior of these highly functionalized ketones does not always match that of structurally similar aldehydes.