(R)-(E)-4-(tributylstannyl)but-3-en-2-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-(E)-4-(tributylstannyl)but-3-en-2-ol
• 化学式: C₁₆H₃₄OSn
• 分子量: 361.155
• InChiKey: JDGHITRWXNGSKV-KWRROICRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  18
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(E)-4-(tributylstannyl)but-3-en-2-ol 在 碘 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 以71%的产率得到(2R,3E)-4-iodobut-3-en-2-ol
  参考文献：
  名称：

  Total Syntheses of the Dihydrofuranonecarboxylate Natural Products Gregatin B and E: Gram-Scale Synthesis of (+)-Gregatin B and Unambiguous Assignment of the Stereostructure of (+)-Gregatin E

  摘要：

  We synthesized the dextrorotatory enantiomers of gregatin B (1.3 g scale) and E, establishing their diene side chains in the last step by Heck coupling with variable iodoolefins. Their counterpart was synthesized in 30% overall yield and with high enantiopurity (97% ee) from benzyl tiglate, beginning with an asymmetric dihydroxylation. The stereostructure of gregatin E followed from HPLC comparisons between the four synthetic stereoisomers of this compound and natural gregatin E, which we isolated from Cadophora gregata.

  DOI：

  10.1021/ol5032602
• 作为产物：
  描述：

  (R)-(+)-3-丁炔-2-醇 、 三正丁基氢锡 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以56%的产率得到(R)-(E)-4-(tributylstannyl)but-3-en-2-ol
  参考文献：
  名称：

  Total Syntheses of the Dihydrofuranonecarboxylate Natural Products Gregatin B and E: Gram-Scale Synthesis of (+)-Gregatin B and Unambiguous Assignment of the Stereostructure of (+)-Gregatin E

  摘要：

  We synthesized the dextrorotatory enantiomers of gregatin B (1.3 g scale) and E, establishing their diene side chains in the last step by Heck coupling with variable iodoolefins. Their counterpart was synthesized in 30% overall yield and with high enantiopurity (97% ee) from benzyl tiglate, beginning with an asymmetric dihydroxylation. The stereostructure of gregatin E followed from HPLC comparisons between the four synthetic stereoisomers of this compound and natural gregatin E, which we isolated from Cadophora gregata.

  DOI：

  10.1021/ol5032602

文献信息

• Total Synthesis of Pancratistatin Relying on the [3,3]-Sigmatropic Rearrangement
  作者：Hyojin Ko、Eunkyung Kim、Jae Eun Park、Deukjoon Kim、Sanghee Kim

  DOI：10.1021/jo035371n

  日期：2004.1.1

  A new total synthesis of the antitumor alkaloid, pancratistatin (1), has been accomplished from readily available starting materials. Claisen rearrangement of the racemic dihydropyranethylene 17 was employed to construct the A and C rings with the appropriate stereochemistry. In addition, the Ireland−Claisen rearrangement of the enantiomerically pure 9 followed by ring-closing metathesis provided the

  抗肿瘤生物碱的新的全合成潘克拉斯汀（1），已经可以从容易获得的起始原料中完成。外消旋二氢吡喃乙烯17的克莱森重排用于构建具有适当立体化学的A和C环。此外，对映体纯9的Ireland-Claisen重排，然后进行闭环复分解，提供了重要的中间体24，这表明我们的方法可以产生（+）-胰抑素的对映选择性合成。带有适当官能化的环己烯24立体和区域控制的官能团互换（例如碘内酯化，二羟基化和环状硫酸盐消除反应）促进了目标天然产物的生产。
• Asymmetric Total Synthesis of Cyclocitrinol
  作者：Junyang Liu、Jianlei Wu、Jian-Hong Fan、Xin Yan、Guangjian Mei、Chuang-Chuang Li

  DOI：10.1021/jacs.8b02629

  日期：2018.4.25

  asymmetric total synthesis of cyclocitrinol, an unusual C25 steroid, has been accomplished in a linear sequence of 18 steps from commercially available compound 11. The synthetically challenging bicyclo[4.4.1] A/B ring system with a strained bridgehead (anti-Bredt) double bond of cyclocitrinol was constructed efficiently and diastereoselectively via a type II intramolecular [5 + 2] cycloaddition.

  环柠檬醇（一种不寻常的 C25 类固醇）的第一个和不对称全合成是从市售化合物 11 以 18 步的线性序列完成的。合成具有挑战性的双环 [4.4.1] A/B 环系统具有紧张的桥头（抗-Bredt) 双键通过 II 型分子内 [5 + 2] 环加成有效且非对映选择性地构建。
• Asymmetric Total Syntheses of (−)-Antofine and (−)-Cryptopleurine Using (<i>R</i>)-(<i>E</i>)-4-(Tributylstannyl)but-3-en-2-ol
  作者：Sanghee Kim、Taeho Lee、Eunjung Lee、Jaekwang Lee、Gao-jun Fan、Sang Kook Lee、Deukjoon Kim

  DOI：10.1021/jo049820a

  日期：2004.4.1

  The asymmetric total syntheses of the representative phenanthroindolizidine and phenanthroquinolizidine alkaloids, (−)-antofine and (−)-cryptopleurine, are described. An efficient synthetic pathway to the key intermediate 12, in enantiomerically pure form, was achieved by using a chiral building block (R)-9 and the Overman rearrangement with a total transfer of chirality. The problem of constructing

  描述了代表性的菲咯啉吲哚和菲咯喹啉嗪生物碱（-）-antofine和（-）-cryptopleurine的不对称总合成。通过使用手性结构单元（R）-9和具有手性的全部转移的Overman重排，可以实现对映体纯形式的通往关键中间体12的有效合成途径。主要通过分别使用闭环易位反应和交叉复分解反应成功地解决了构建吡咯烷环和哌啶环的问题。
• Total Syntheses of the Dihydrofuranonecarboxylate Natural Products Gregatin B and E: Gram-Scale Synthesis of (+)-Gregatin B and Unambiguous Assignment of the Stereostructure of (+)-Gregatin E
  作者：Fabian Weber、Reinhard Brückner

  DOI：10.1021/ol5032602

  日期：2014.12.19

  We synthesized the dextrorotatory enantiomers of gregatin B (1.3 g scale) and E, establishing their diene side chains in the last step by Heck coupling with variable iodoolefins. Their counterpart was synthesized in 30% overall yield and with high enantiopurity (97% ee) from benzyl tiglate, beginning with an asymmetric dihydroxylation. The stereostructure of gregatin E followed from HPLC comparisons between the four synthetic stereoisomers of this compound and natural gregatin E, which we isolated from Cadophora gregata.