(S)-1-(Tetrahydro-pyran-2-yloxy)-5-trimethylsilanyl-pent-4-yn-2-ol | 186692-76-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (S)-1-(Tetrahydro-pyran-2-yloxy)-5-trimethylsilanyl-pent-4-yn-2-ol
• CAS: 186692-76-2
• 化学式: C₁₃H₂₄O₃Si
• 分子量: 256.417
• InChiKey: MSZLFEJQCBVOQJ-UEWDXFNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.16
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-1-(Tetrahydro-pyran-2-yloxy)-5-trimethylsilanyl-pent-4-yn-2-ol 在 四丙基高钌酸铵 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 正丁基锂 、 草酰氯 、 4 A molecular sieve 、 三氟化硼乙醚 、 bis(cyclohexanyl)borane 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 silver nitrate 、 溶剂黄146 、 二甲基亚砜 、 苯硫酚 、 N-甲基吗啉氧化物 、 三乙胺 、 N,N-二异丙基乙胺 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 9.25h， 生成
  参考文献：
  名称：

  Total Syntheses of Epothilones A and B

  摘要：

  Convergent, stereocontrolled total syntheses of the microtubule-stabilizing macrolides epothilones A (2) and B (3) have been achieved. Four distinct ring-forming strategies were pursued (see Scheme 1). Of these four, three were reduced to practice. In one approach, the action of a base on a substance possessing an acetate ester and a nonenolizable aldehyde brought about a remarkably effective macroaldolization see (89 --> 90 + 91; 99 --> 100 + 101), simultaneously creating the C2-C3 bond and the hydroxyl-bearing stereocenter at C-3. Alternatively, the 16-membered macrolide of the epothilones could be fashioned through a C12-C13 ring-closing olefin metathesis (e.g. see 111 --> 90 + 117; 122 --> 105 + 123) and through macrolactonization of the appropriate hydroxy acid (e.g. see 88 --> 93). The application of a stereospecific B-alkyl Suzuki coupling strategy permitted the establishment of a cis C12-C13 olefin, thus setting the stage for an eventual site-and diastereoselective epoxidation reaction (see 96 --> 2; 106 --> 3). The development of a novel cyclopropane solvolysis strategy for incorporating the geminal methyl groups of the epothilones (see 39 --> 40 --> 41), and the use of Lewis acid catalyzed diene-aldehyde cyclocondensation (LACDAC) (see 35 + 36 --> 37) and asymmetric allylation (see 10 --> 76) methodology are also noteworthy.

  DOI：

  10.1021/ja971946k
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 alkaline earth salt of/the/ methylsulfuric acid 在 三氟化硼乙醚 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (S)-1-(Tetrahydro-pyran-2-yloxy)-5-trimethylsilanyl-pent-4-yn-2-ol
  参考文献：
  名称：

  Total Syntheses of Epothilones A and B

  摘要：

  Convergent, stereocontrolled total syntheses of the microtubule-stabilizing macrolides epothilones A (2) and B (3) have been achieved. Four distinct ring-forming strategies were pursued (see Scheme 1). Of these four, three were reduced to practice. In one approach, the action of a base on a substance possessing an acetate ester and a nonenolizable aldehyde brought about a remarkably effective macroaldolization see (89 --> 90 + 91; 99 --> 100 + 101), simultaneously creating the C2-C3 bond and the hydroxyl-bearing stereocenter at C-3. Alternatively, the 16-membered macrolide of the epothilones could be fashioned through a C12-C13 ring-closing olefin metathesis (e.g. see 111 --> 90 + 117; 122 --> 105 + 123) and through macrolactonization of the appropriate hydroxy acid (e.g. see 88 --> 93). The application of a stereospecific B-alkyl Suzuki coupling strategy permitted the establishment of a cis C12-C13 olefin, thus setting the stage for an eventual site-and diastereoselective epoxidation reaction (see 96 --> 2; 106 --> 3). The development of a novel cyclopropane solvolysis strategy for incorporating the geminal methyl groups of the epothilones (see 39 --> 40 --> 41), and the use of Lewis acid catalyzed diene-aldehyde cyclocondensation (LACDAC) (see 35 + 36 --> 37) and asymmetric allylation (see 10 --> 76) methodology are also noteworthy.

  DOI：

  10.1021/ja971946k

文献信息

• Total Synthesis of (−)-Amphidinolide K
  作者：Haye Min Ko、Chung Whan Lee、Hyung Kyoo Kwon、Hea Seung Chung、Soo Young Choi、Young Keun Chung、Eun Lee

  DOI：10.1002/anie.200805266

  日期：2009.3.16

  reaction of an alkynyl boronate with an alkene derivative as well as a radical cyclization reaction of a homopropargylic β‐alkoxyacrylate are the key transformations in the total synthesis of the cytotoxic macrolide (−)‐amphidinolide K.

  大环内酯的神奇之处：炔基硼酸酯与烯烃衍生物的烯炔交叉复分解反应以及均丙基β-烷氧基丙烯酸酯的自由基环化反应是细胞毒性大环内酯（-）-两性内酯K合成的关键转变。