anti-3-(phenylhydroxymethyl)-3-methyl-5-pentanone | 120501-81-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: anti-3-(phenylhydroxymethyl)-3-methyl-5-pentanone
• 英文别名: (3RS,1'SR)-3-((Hydroxyphenyl)methyl)-3-methylpentan-2-one；(3S)-3-[(S)-hydroxy(phenyl)methyl]-3-methylpentan-2-one
• CAS: 120501-81-7；120501-82-8；132645-98-8；132645-99-9
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: QCWIYWNEPNUYQR-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  惕格酸 在 bis(cyclohexanyl)borane 作用下， 以 四氢呋喃 为溶剂， 反应 23.0h， 生成 anti-3-(phenylhydroxymethyl)-3-methyl-5-pentanone
  参考文献：
  名称：

  A new protocol for regio- and stereocontrolled aldol reactions through the conjugate addition of dialkylboranes to .alpha.,.beta.-unsaturated ketones

  摘要：

  A one-pot, two-step procedure, consisting of the 1,4-addition of dialkylboranes to beta-substituted (E)-alpha,beta-unsaturated ketones followed by the reaction of the resulting configurationally pure (Z)-(vinyloxy)boranes with aldehydes, is reported. The overall process corresponds to a regio- and stereocontrolled aldol addition of an unsymmetrical ketone to an aldehyde. A concerted 1,4-addition mechanism accounts for the stereochemical outcome of the hydroboraton reaction; cyclic enones do not undergo conjugate addition, while (Z)-beta-substituted or beta,beta-disubstituted alpha,beta-unsaturated ketones still react in a 1,4-fashion, but with a slower rate and a lower degree of chemoselectivity with respect to beta-substituted (E)-alpha,beta-unsaturated ketones. In the cases of alpha,beta-disubstituted alpha,beta-unsaturated ketones and (E)-(S-phenylthio)cinnammate, which react with dicyclohexylborane to give a mixture of E and Z enolates, an alternative mechanism is proposed.

  DOI：

  10.1021/jo00020a025

文献信息

• Stereochemistry of the fluoride catalyzed aldol reaction of enol silyl ethers. Evidence for another non-chelate transition state
  作者：Eiichi Nakamura、Shigeru Yamago、Daisuke Machii、Isao Kuwajima

  DOI：10.1016/s0040-4039(00)86713-1

  日期：——
• Simple diastereoselectivity of the aldol reaction of persubstituted enolates. Stereoselective construction of quaternary centers
  作者：Shigeru Yamago、Daisuke Machii、Eiichi Nakamura

  DOI：10.1021/jo00006a026

  日期：1991.3

  Simple diastereoselectivity of several important categories of aldol reactions of persubstituted enolates has been investigated for sterically least biased cyclic and acyclic ketone and aldehyde enolates, 1-4, and has been found to be useful for the stereoselective construction of quaternary carbon centers. The types of reactions examined involve the reaction of lithium, borinate, borate, trialkoxytitanium, trichlorotitanium, and zirconium (Cp2ZrCl) enolates, and the reactions of enol silyl ethers under high pressure, fluoride catalysis, and Lewis acid catalysis. In contrast to the less substituted metal enolates, uncatalyzed reactions of persubstituted metal enolates proceeded in a sense anticipated from the conventional Zimmerman-Traxler chair transition state (TS) model. The fluoride-catalyzed reaction of the cyclic enolate 1a showed stereoselectivity consistent with the open extended TS, while enolates 2a-4a showed anomalous behavior. The selectivity of the Lewis acid mediated aldol reaction of enol silyl ethers was found to be dependent on the Lewis acid used, and the BF3.Et2O-mediated reaction of 2a and 3a showed maximum selectivity in a sense predicted by the chair TS. The stereostructures of the aldols have been determined by single-crystal X-ray analysis or by chemical correlations.