5-(Dimethylthexylsiloxy)pentan-2-one

• 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: 5-(Dimethylthexylsiloxy)pentan-2-one
• 英文别名: 5-[2,3-Dimethylbutan-2-yl(dimethyl)silyl]oxypentan-2-one
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: DPEPCADQJSYIGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  diethyl-2-(cyclohexylimino)vinyl phosphonate 、 5-(Dimethylthexylsiloxy)pentan-2-one 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 (Z)-3-Methyl-6-(dimethylthexylsiloxy)hex-2-enal 、 (E)-3-Methyl-6-(dimethylthexylsiloxy)hex-2-enal
  参考文献：
  名称：

  Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations

  摘要：

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.

  DOI：

  10.1021/jo00080a030
• 作为产物：
  描述：

  5-羟基-2-戊酮 、 二甲基叔己基氯化硅 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以79%的产率得到5-(Dimethylthexylsiloxy)pentan-2-one
  参考文献：
  名称：

  Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations

  摘要：

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.

  DOI：

  10.1021/jo00080a030

文献信息

• Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations
  作者：Lutz F. Tietze、Holger Geissler、Jens Fennen、Thomas Brumby、Siegbert Brand、Gerhard Schulz

  DOI：10.1021/jo00080a030

  日期：1994.1

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.