[(2-pyridyldimethylsilyl)benzyl]trimethylsilane

• 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: [(2-pyridyldimethylsilyl)benzyl]trimethylsilane
• 英文别名: Dimethyl-[phenyl(trimethylsilyl)methyl]-pyridin-2-ylsilane
• 化学式: C₁₇H₂₅NSi₂
• 分子量: 299.563
• InChiKey: AEFLSNNUKMDARA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 [(2-pyridyldimethylsilyl)methyl]benzene 在 叔丁基锂 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 0.5h， 生成 [(2-pyridyldimethylsilyl)benzyl]trimethylsilane 、 [[2-pyridyl(benzyl)methylsilyl]methyl]trimethylsilane
  参考文献：
  名称：

  Pyridyl Group Assisted Deprotonation of a Methyl Group on Silicon:  Complex Induced Proximity Effect and Novel Hydroxymethylation

  摘要：

  A novel methodology for the deprotonation of a methyl group on silicon has been developed. This newly developed cr-lithiation protocol is based on the intramolecular pyridyl group coordination to stabilize the a-silyl carbanion together with the inherent silicon a effect. It was found that the deprotonation (t-BuLi/Et(2)O/-78 degreesC) occurs with 2-pyridyltrimethylsilane but not with other related silanes such as phenyltrimethylsilane, 3-pyridyltrimethylsilane, and 4-pyridyltrimethylsilane. It seems that this deprotonation proceeded through the agency of the complex-induced proximity effect (CIPE) of a 2-pyridyl group on silicon. (1)H NMR analysis of (2-pyridyldimethylsilyl)methyllithium revealed the intramolecular coordination of a pyridyl group to lithium. ( 2-Pyridyldimethylsilyl)-methyllithium was found to react with chlorosilanes, hydrosilanes, chlorostannanes, bromine, iodine, organic bromides, aldehydes, and ketones in good to excellent yields. The resultant adducts were further oxidized with H(2)O(2)/KF to give the corresponding alcohols in excellent yields. Thus, this two-step transformation provides an efficient method for the nucleophilic hydroxymethylation.

  DOI：

  10.1021/jo015528g

文献信息

• Pyridyl Group Assisted Deprotonation of a Methyl Group on Silicon:  Complex Induced Proximity Effect and Novel Hydroxymethylation
  作者：Kenichiro Itami、Toshiyuki Kamei、Koichi Mitsudo、Toshiki Nokami、Jun-ichi Yoshida

  DOI：10.1021/jo015528g

  日期：2001.6.1

  A novel methodology for the deprotonation of a methyl group on silicon has been developed. This newly developed cr-lithiation protocol is based on the intramolecular pyridyl group coordination to stabilize the a-silyl carbanion together with the inherent silicon a effect. It was found that the deprotonation (t-BuLi/Et(2)O/-78 degreesC) occurs with 2-pyridyltrimethylsilane but not with other related silanes such as phenyltrimethylsilane, 3-pyridyltrimethylsilane, and 4-pyridyltrimethylsilane. It seems that this deprotonation proceeded through the agency of the complex-induced proximity effect (CIPE) of a 2-pyridyl group on silicon. (1)H NMR analysis of (2-pyridyldimethylsilyl)methyllithium revealed the intramolecular coordination of a pyridyl group to lithium. ( 2-Pyridyldimethylsilyl)-methyllithium was found to react with chlorosilanes, hydrosilanes, chlorostannanes, bromine, iodine, organic bromides, aldehydes, and ketones in good to excellent yields. The resultant adducts were further oxidized with H(2)O(2)/KF to give the corresponding alcohols in excellent yields. Thus, this two-step transformation provides an efficient method for the nucleophilic hydroxymethylation.