(R,R)-Hydrobenzoin bis-(R)-3-cyclohexenecarboxylate | 171011-76-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (R,R)-Hydrobenzoin bis-(R)-3-cyclohexenecarboxylate
• 英文别名: [(1R,2R)-2-[(1R)-cyclohex-3-ene-1-carbonyl]oxy-1,2-diphenylethyl] (1R)-cyclohex-3-ene-1-carboxylate
• CAS: 171011-76-0
• 化学式: C₂₈H₃₀O₄
• 分子量: 430.544
• InChiKey: JXCTZLREJUHBDG-QEGGNFSNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R,R)-Hydrobenzoin bis-(R)-3-cyclohexenecarboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (R)-(+)-cyclohex-3-ene-1-methanol 、 (S)-4-(羟甲基)环己烯
  参考文献：
  名称：

  Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506

  摘要：

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.

  DOI：

  10.1021/jo00127a031
• 作为产物：
  描述：

  氢胺 在 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 72.33h， 生成 (R,R)-Hydrobenzoin bis-(R)-3-cyclohexenecarboxylate
  参考文献：
  名称：

  Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506

  摘要：

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.

  DOI：

  10.1021/jo00127a031

文献信息

• Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506
  作者：James A. Marshall、Shiping Xie

  DOI：10.1021/jo00127a031

  日期：1995.11

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.