(+/-)-3-(trimethylsilyl)-3,4-pentadien-2-ol | 129571-79-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-3-(trimethylsilyl)-3,4-pentadien-2-ol
• CAS: 129571-79-5
• 化学式: C₈H₁₆OSi
• 分子量: 156.3
• InChiKey: PIRFTHZRZOKTFT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  乙酸乙烯酯 、 (+/-)-3-(trimethylsilyl)-3,4-pentadien-2-ol 在 molecular sieve 作用下， 以 正己烷 为溶剂， 反应 120.0h， 以45%的产率得到Acetic acid (R)-1-methyl-2-trimethylsilanyl-buta-2,3-dienyl ester
  参考文献：
  名称：

  Kinetic resolutions of chiral unsaturated alcohols that cannot be resolved efficiently via enantioselective epoxidation

  摘要：

  DOI：

  10.1021/ja00176a076
• 作为产物：
  描述：

  1-(三甲基硅基)丙炔 、 乙醛 在 titanium(IV) isopropylate 、 叔丁基锂 作用下， 生成 (+/-)-3-(trimethylsilyl)-3,4-pentadien-2-ol
  参考文献：
  名称：

  Enantioselective esterifications of unsaturated alcohols mediated by a lipase prepared from Pseudomonas sp

  摘要：

  Competition experiments and measurements of enantioselectivities were used to develop a simple active-site model (Figure 1) for resolutions of beta-hydroxy-alpha-methylene carbonyl compounds III via acyl transfers mediated by lipase from Pseudomonas sp. (AK). Further experiments were used to test and refine this model with respect to resolutions of allylic, propargylic, homopropargylic, and other alcohols (Tables I-IV, respectively). The model proved extremely reliable for predicting the sense of the asymmetric induction, and the combined data collected in this paper give an indication of what structural features of the substrates can be correlated with high enantioselectivities in these resolutions. Furthermore, the results account for the conspicuous reversal of enantioselectivity previously observed in resolutions of gamma-hydroxy-alpha,beta-unsaturated esters 35. Kinetic resolutions of two substrates (allenol 14 and dienol 9) via asymmetric epoxidations were performed for comparison with the methodology presented in this paper.

  DOI：

  10.1021/ja00016a032

文献信息

• Nonracemic α-Allenyl Carbinols from Asymmetric Propargylation with the 10-Trimethylsilyl-9-borabicyclo[3.3.2]decanes
  作者：Eliud Hernandez、John A. Soderquist

  DOI：10.1021/ol051886k

  日期：2005.11.1

  [reaction: see text] The asymmetric propargylboration of aldehydes at -78 degrees C in <3 h with 1 provides silylated alpha-allenyl carbinols 6 (60-87%) in high ee (94% to >98% ee). The reagents 1 are easily prepared in both enantiomeric forms with a simple Grignard procedure and air-stable borinate complexes 2. The ozonolysis of 6 proceeds smoothly through an acylsilane intermediate to give a TMS

  [反应：参见正文]醛在-78摄氏度下于<3 h内与1进行的不对称炔丙基硼化可在高ee（94％至> 98％ee）中提供甲硅烷基化的α-烯基甲醇6（60-87％）。试剂1可以通过简单的格氏试剂和对空气稳定的硼酸酯络合物2轻松制备成对映体形式。6的臭氧分解反应通过酰基硅烷中间体平稳进行，得到TMS酯，该酯被水解成α-羟基酸。水。
• Kinetic resolutions of chiral unsaturated alcohols that cannot be resolved efficiently via enantioselective epoxidation
  作者：Kevin Burgess、Lee D. Jennings

  DOI：10.1021/ja00176a076

  日期：1990.9
• Enantioselective esterifications of unsaturated alcohols mediated by a lipase prepared from Pseudomonas sp
  作者：Kevin Burgess、Lee D. Jennings

  DOI：10.1021/ja00016a032

  日期：1991.7

  Competition experiments and measurements of enantioselectivities were used to develop a simple active-site model (Figure 1) for resolutions of beta-hydroxy-alpha-methylene carbonyl compounds III via acyl transfers mediated by lipase from Pseudomonas sp. (AK). Further experiments were used to test and refine this model with respect to resolutions of allylic, propargylic, homopropargylic, and other alcohols (Tables I-IV, respectively). The model proved extremely reliable for predicting the sense of the asymmetric induction, and the combined data collected in this paper give an indication of what structural features of the substrates can be correlated with high enantioselectivities in these resolutions. Furthermore, the results account for the conspicuous reversal of enantioselectivity previously observed in resolutions of gamma-hydroxy-alpha,beta-unsaturated esters 35. Kinetic resolutions of two substrates (allenol 14 and dienol 9) via asymmetric epoxidations were performed for comparison with the methodology presented in this paper.