syn-4-(phenylhydroxymethyl)-3-hexanone | 92694-77-4

• 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: syn-4-(phenylhydroxymethyl)-3-hexanone
• 英文别名: (4S)-4-[(S)-hydroxy(phenyl)methyl]hexan-3-one
• CAS: 92694-77-4；132455-66-4；134526-26-4；134526-27-5；135266-68-1
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: ZKIFEFLNXCVHAC-DGCLKSJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  5
• 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：

  (C6H11)2(OC(Et)CHCH2Me)borane 、 苯甲醛 在 水 作用下， 以 氯仿 为溶剂， 以57%的产率得到syn-4-(phenylhydroxymethyl)-3-hexanone
  参考文献：
  名称：

  通过（E）-α，β-不饱和酮的1,4加氢硼化制得（Z）-乙烯基氧基硼烷的新方法。合成合成羟醛

  摘要：

  （Z）-乙烯基氧基硼烷是通过在20°C下于四氢呋喃，CH 2 Cl 2或CHCl 3中将无环二取代的（E）-α，β-不饱和酮与二环己基硼烷或二异樟脑环硼烷进行1,4-氢硼化而制得的; 用醛处理加氢硼化混合物可使用后者的硼烷以高收率和极佳的对映体过量合成纯的合成醇醛。

  DOI：

  10.1039/c39900001680

文献信息

• Stereoselective 1,4-hydroboration of acyclic (E)-α,β-unsaturated ketones with dialkylboranes. Synthesis of (Z)-vinyloxyboranes.
  作者：Gian Paolo Boldrini、Michele Bortolotti、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1016/s0040-4039(00)92052-5

  日期：1991.2

  Dialkylboranes add to acyclic disubstituted (E)-α,β-unsaturated ketones in a 1,4-fashion affording (Z)-vinyloxyboranes as major or sole products. The stereochemical outcome of the hydroboration reaction is consistent with a concerted pericyclic mechanism. The intermediate vinyloxyboranes can be trapped with aldehydes to give virtually pure syn β-hydroxyketones.

  二烷基硼烷以1，4-方式加到无环二取代的（E）-α，β-不饱和酮中，提供（Z）-乙烯基氧基硼烷作为主要或唯一产物。硼氢化反应的立体化学结果与一致的周环机制一致。中间体乙烯基氧基硼烷可以被醛捕获，从而得到实际上纯的顺式β-羟基酮。
• A new protocol for regio- and stereocontrolled aldol reactions through the conjugate addition of dialkylboranes to .alpha.,.beta.-unsaturated ketones
  作者：Gian Paolo Boldrini、Michele Bortolotti、Fabrizio Mancini、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1021/jo00020a025

  日期：1991.9

  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.
• A new approach to (Z)-vinyloxyboranes via 1,4 hydroboration of (E)-α,β-unsaturated ketones. Synthesis of syn aldols
  作者：Gian Paolo Boldrini、Fabrizio Mancini、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1039/c39900001680

  日期：——

  (Z)-Vinyloxy boranes are obtained via 1,4-hydroboration of acyclic disubstituted (E)-α,β-unsaturated ketones with dicyclohexylborane or diisopinocampheylborane in tetrahydrofuran, CH2Cl2 or CHCl3 at 20 °C; treatment of the hydroboration mixture with an aldehyde allows pure syn aldols to be synthesized in good yields, and in excellent enantiomeric excesses, using the latter borane.

  （Z）-乙烯基氧基硼烷是通过在20°C下于四氢呋喃，CH 2 Cl 2或CHCl 3中将无环二取代的（E）-α，β-不饱和酮与二环己基硼烷或二异樟脑环硼烷进行1,4-氢硼化而制得的; 用醛处理加氢硼化混合物可使用后者的硼烷以高收率和极佳的对映体过量合成纯的合成醇醛。