(2E,2R,3R,4S,5S)-4,6-Dimethyl-2,3-epoxy-5-<(p-methoxybenzyl)oxy>-7-<(1R,3R,4R)-3-methoxy-4-<(triisopropylsilyl)oxy>cyclohexyl>-2,6-heptadien-1-ol | 171011-81-7

• 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: (2E,2R,3R,4S,5S)-4,6-Dimethyl-2,3-epoxy-5-<(p-methoxybenzyl)oxy>-7-<(1R,3R,4R)-3-methoxy-4-<(triisopropylsilyl)oxy>cyclohexyl>-2,6-heptadien-1-ol
• 英文别名: [(2R,3R)-3-[(E,2S,3S)-3-[(4-methoxyphenyl)methoxy]-5-[(1R,3R,4R)-3-methoxy-4-tri(propan-2-yl)silyloxycyclohexyl]-4-methylpent-4-en-2-yl]oxiran-2-yl]methanol
• CAS: 171011-81-7
• 化学式: C₃₃H₅₆O₆Si
• 分子量: 576.89
• InChiKey: NTCIOCYEFIUDCV-RGRONJBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  40
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  69.7
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2E,2R,3R,4S,5S)-4,6-Dimethyl-2,3-epoxy-5-<(p-methoxybenzyl)oxy>-7-<(1R,3R,4R)-3-methoxy-4-<(triisopropylsilyl)oxy>cyclohexyl>-2,6-heptadien-1-ol 在 molecular sieve 、 sodium dihydro-bis-(2-methoxyethoxy)aluminate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 20.5h， 生成 <2S-<2α,4α,5α,6α>>-2-(4-Methoxyphenyl)-6-<2-<3-methoxy-4-<oxy>cyclohexyl>-1-methylethenyl>-5-methyl-1,3-dioxane-4-ethanol
  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：

  2,2,2-三氯代亚氨逐乙酸-4-甲氧基苄酯 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 molecular sieve 、 D-(-)-酒石酸二乙酯 、 三氟甲磺酸 、 sodium dihydro-bis-(2-methoxyethoxy)aluminate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 30.83h， 生成 (2E,2R,3R,4S,5S)-4,6-Dimethyl-2,3-epoxy-5-<(p-methoxybenzyl)oxy>-7-<(1R,3R,4R)-3-methoxy-4-<(triisopropylsilyl)oxy>cyclohexyl>-2,6-heptadien-1-ol
  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.