(1R,2R,5R)-2-iodo-7-oxabicyclo[3.2.1]octan-6-one | 119719-61-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1R,2R,5R)-2-iodo-7-oxabicyclo[3.2.1]octan-6-one
• 英文别名: (1R,4R)-4-iodo-6-oxabicyclo[3.2.1]octan-7-one
• CAS: 119719-61-8
• 化学式: C₇H₉IO₂
• 分子量: 252.052
• InChiKey: ALVFLEWPYOOJPZ-QYRBDRAASA-N

物化性质

• 熔点：
  135-136 °C
• 沸点：
  349.7±25.0 °C(Predicted)
• 密度：
  1.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R,5R)-2-iodo-7-oxabicyclo[3.2.1]octan-6-one 在 sodium hydroxide 、 2,6-二叔丁基-4-甲基吡啶 、 硼烷四氢呋喃络合物 、 双氧水 、 碳酸氢钠 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 41.67h， 生成 (1R,3R,4R) methyl 4-hydroxy-3-methoxy-1-cyclohexanecarboxylate
  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：

  3-环己烯-1-甲酸 在 碘 、 碳酸氢钠 、 potassium iodide 作用下， 反应 24.0h， 以86%的产率得到(1R,2R,5R)-2-iodo-7-oxabicyclo[3.2.1]octan-6-one
  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

• Synthetic studies on the immunosuppressive agent FK-506: Enantioselective synthesis of a C22C34 fragment
  作者：Robert K. Baker、Kathleen M. Rupprecht、David M. Armistead、Joshua Boger、Robert A. Frankshun、Paul J. Hodges、Karst Hoogsteen、Judith M. Pissano、Bruce E. Witzel

  DOI：10.1016/s0040-4039(97)10532-9

  日期：1998.1

  The C28C32 cyclohexyl group of the natural product, FK-506, was prepared enantioselectively from the iodolactone by replacement of iodide with retention of configuration. The C27C28 trisubstituted olefin was introduced stereoselectively via a classical aldol/elimination sequence employing titanium enolate methodology. Elaboration of this chemistry has led to a synthesis of a C22C34 fragment of the

  天然产物FK-506的C28C32环己基是由碘内酯对映选择性制备的，方法是在保留构型的情况下替换碘化物。使用烯醇钛方法通过经典的羟醛/消除序列立体选择性地引入C27 ＝ C28三取代的烯烃。对这种化学方法的详细说明导致合成了天然产物的C22C34片段。
• Application of nitrile oxide cycloadditions to a convergent, asymmetric synthesis of (+)-phyllanthocin
  作者：Stephen F. Martin、John A. Colapret、Michael S. Dappen、Brian Dupre、Christopher J. Murphy

  DOI：10.1021/jo00270a035

  日期：1989.4