1-[4-[[Dimethyl(phenyl)silyl]methyl]cyclohex-3-en-1-yl]ethanone | 187801-09-8

• 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: 1-[4-[[Dimethyl(phenyl)silyl]methyl]cyclohex-3-en-1-yl]ethanone
• CAS: 187801-09-8
• 化学式: C₁₇H₂₄OSi
• 分子量: 272.462
• InChiKey: ZXUFZEIVLHGNRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-[4-[[Dimethyl(phenyl)silyl]methyl]cyclohex-3-en-1-yl]ethanone 在 二甲基氯化铝 、 四氯化钛 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 31.0h， 生成 1-((1R,5R)-5-Acetyl-2-methylene-cyclohexyl)-propan-1-one
  参考文献：
  名称：

  Tandem Transformations Involving Allylic Silanes. 2. Highly Diastereoselective Substitutions Involving [(Trialkylsilyl)methyl]cyclohexene Derivatives with Aldehydes. Synthetic Studies on the Problem of Lewis Acid-Promoted Protodesilylation and Enolization

  摘要：

  Diels-Alder cycloaddition of 2-[(trialkylsilyl)methyl]-1,3-butadienes with a variety of dienophiles and substitution reactions between these allylsilane-containing adducts and aldehyde or acid chloride electrophiles have been combined into ''tandem sequential reactions.'' These tandem sequences proceed with equal or greater yield (50-80%) than the reactions performed separately with no decrease in regio- or stereoselectivity. The sequence produces cyclic compounds with three or four stereogenic centers with good to excellent diastereoselectivity from three simple, noncyclic, and achiral reaction partners. Unprecedented levels of diastereoselectivity (de > 93%) have been achieved in allylic substitution reactions involving substituted [(trialkylsilyl)methyl]cyclohexene derivatives with aldehyde electrophiles. During the course of these studies, protodesilylation of allylsilanes has been investigated in detail, and a cocatalyst system of TiCl4 and Me2AlCl has been developed that has eliminated silicon loss in the substitution reactions studied. Lewis acid-promoted enolization of ester and ketone substrates with chiral centers adjacent to the carbonyl moiety has been studied also. It has been shown that this event in our studies occurs primarily during catalyst quench. This isomerization is prevented by quenching the catalyst with a Lewis base, such as methanol or triethylamine, prior to aqueous workup.

  DOI：

  10.1021/jo970821v
• 作为产物：
  描述：

  magnesium,methanidyl-dimethyl-phenylsilane,chloride 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 二甲基氯化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 1-[4-[[Dimethyl(phenyl)silyl]methyl]cyclohex-3-en-1-yl]ethanone
  参考文献：
  名称：

  Noncascade Tandem Transformations Involving Allylic Silanes. 1. Pericyclic and Ionic Reactions Combined into “One-Pot” Sequences

  摘要：

  DOI：

  10.1021/jo962025f

文献信息

• Tandem Transformations Involving Allylic Silanes. 2. Highly Diastereoselective Substitutions Involving [(Trialkylsilyl)methyl]cyclohexene Derivatives with Aldehydes. Synthetic Studies on the Problem of Lewis Acid-Promoted Protodesilylation and Enolization
  作者：Michael G. Organ、Derick D. Winkle、John Huffmann

  DOI：10.1021/jo970821v

  日期：1997.8.1

  Diels-Alder cycloaddition of 2-[(trialkylsilyl)methyl]-1,3-butadienes with a variety of dienophiles and substitution reactions between these allylsilane-containing adducts and aldehyde or acid chloride electrophiles have been combined into ''tandem sequential reactions.'' These tandem sequences proceed with equal or greater yield (50-80%) than the reactions performed separately with no decrease in regio- or stereoselectivity. The sequence produces cyclic compounds with three or four stereogenic centers with good to excellent diastereoselectivity from three simple, noncyclic, and achiral reaction partners. Unprecedented levels of diastereoselectivity (de > 93%) have been achieved in allylic substitution reactions involving substituted [(trialkylsilyl)methyl]cyclohexene derivatives with aldehyde electrophiles. During the course of these studies, protodesilylation of allylsilanes has been investigated in detail, and a cocatalyst system of TiCl4 and Me2AlCl has been developed that has eliminated silicon loss in the substitution reactions studied. Lewis acid-promoted enolization of ester and ketone substrates with chiral centers adjacent to the carbonyl moiety has been studied also. It has been shown that this event in our studies occurs primarily during catalyst quench. This isomerization is prevented by quenching the catalyst with a Lewis base, such as methanol or triethylamine, prior to aqueous workup.
• Noncascade Tandem Transformations Involving Allylic Silanes. 1. Pericyclic and Ionic Reactions Combined into “One-Pot” Sequences
  作者：Michael G. Organ、Derick D. Winkle

  DOI：10.1021/jo962025f

  日期：1997.3.1