(R)-4-<(tert-Butyldimethylsilyl)oxy>-2-pentynyl 1,1,1-trimethylacetate | 171011-71-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-4-<(tert-Butyldimethylsilyl)oxy>-2-pentynyl 1,1,1-trimethylacetate
• 英文别名: [(4R)-4-[tert-butyl(dimethyl)silyl]oxypent-2-ynyl] 2,2-dimethylpropanoate
• CAS: 171011-71-5
• 化学式: C₁₆H₃₀O₃Si
• 分子量: 298.498
• InChiKey: BCRSCZQWLFWAEE-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-4-<(tert-Butyldimethylsilyl)oxy>-2-pentynyl 1,1,1-trimethylacetate 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (R)-1-Methyl-4-(1,1,1-trimethylacetoxy)-2-butynyl methanesulfonate
  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：

  (R)-2-(叔丁基-二甲基-锡氧基)-丙醛 在 4-二甲氨基吡啶 、 正丁基锂 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 10.5h， 生成 (R)-4-<(tert-Butyldimethylsilyl)oxy>-2-pentynyl 1,1,1-trimethylacetate
  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

• GENERATION OF NONRACEMIC 2-(t-BUTYLDIMETHYLSILYLOXY)-3-BUTYNYLLITHIUM FROM (S)-ETHYL LACTATE:
  作者：Marshall, James A.、Yanik, Mathew M.、Adams, Nicholas D.、Ellis, Keith C.、Chobanian, Harry R.、Gudipati, Venugopal、Turner, Tiffany、Curran, Dennis P.

  DOI：10.15227/orgsyn.081.0157

  日期：——
• 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.