syn-4-hydroxy-3-<(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl>-4-phenyl-2-butanone | 132455-68-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: syn-4-hydroxy-3-<(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl>-4-phenyl-2-butanone
• 英文别名: (3R,4R)-4-hydroxy-3-(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl-4-phenylbutan-2-one；(3R,4R)-4-hydroxy-4-phenyl-3-[(2,6,6-trimethylcyclohexen-1-yl)methyl]butan-2-one
• CAS: 132455-68-6
• 化学式: C₂₀H₂₈O₂
• 分子量: 300.441
• InChiKey: LNIYSDGSTJISDR-HKUYNNGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  beta-紫罗酮 、 苯甲醛 在 三氯硅烷 、 2,2'-双(二苯基氧膦)-1,1'-联萘 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 以67%的产率得到syn-4-hydroxy-3-<(2,6,6-trimethyl-1-cyclohexen-1-yl)methyl>-4-phenyl-2-butanone
  参考文献：
  名称：

  使用三氯硅烷，路易斯碱催化的共轭还原和α，β-不饱和酮的还原性醛醇缩合反应。

  摘要：

  Lewis碱（例如Ph3P = O和HMPA）催化三氯硅烷对α，β-不饱和酮的1,4-还原，并且由于在这种条件下几乎不进行醛的1,2-还原，因此与醛的一锅还原醛醇缩合反应成功实现；使用手性路易斯碱的初步研究表明，对映选择性催化的潜力很大。

  DOI：

  10.1039/b807529h

文献信息

• 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。
• Diastereo- and Enantioselective Reductive Aldol Reaction with Trichlorosilane Using Chiral Lewis Bases as Organocatalysts
  作者：Masaharu Sugiura、Norimasa Sato、Yuko Sonoda、Shunsuke Kotani、Makoto Nakajima

  DOI：10.1002/asia.200900450

  日期：2010.3.1

  Chiral Lewis base organocatalysts activate trichlorosilane to promote the tandem conjugate reduction/aldol reaction of α,β‐unsaturated ketones with aldehydes to give optically active β‐hydroxy ketones with good to high syn diastereo‐ and enantioselectivities. The reaction tolerates α,β‐unsaturated aldehydes owing to the chemoselective conjugate reduction of enones in the presence of enals.

  手性路易斯碱的有机催化剂激活三氯硅烷促进串联共轭还原/α的醛醇缩合反应，β不饱和酮与醛，得到具有良好的高光学活性的β羟基酮顺diastereo-和对映选择性。由于在烯醛存在下烯酮的化学选择性共轭还原，该反应可耐受α，β-不饱和醛。
• Direct covalent immobilizaion of chiral phosphine oxide: Hollow mesoporous polystyrene nanospheres as a platform for efficient heterogeneous enantioselective reductive aldol reaction
  作者：Zuyun Yin、Jie Liu、Jianing Zhang、Xuebing Ma

  DOI：10.1016/j.mcat.2023.113363

  日期：2023.8

  with a thin and mesoporous shell suitable for fast mass transfer of reactants and products. In the asymmetric reductive aldol reaction of α, β-unsaturated ketones and benzaldehydes with HSiCl3, HMPNs@BINAPO shows the comparable good to excellent catalytic performances to homogeneous BINAPO and good reusability without an obvious decrease in diastereoselectivity and enantioselectivity.

  昂贵的手性氧化膦的多相催化由于其体积庞大而受到多步骤繁琐的固定化和有限的传质的困扰。在本文中，开发了一种简单直接的策略，将（S）-2,2′-双（二苯基膦）-1,1′-二氧化联萘（BINAPO）共价锚定到中空介孔聚苯乙烯纳米球（HMPN）上来制造HMPN通过一锅 Friedel-Crafts 烷基化支持 BINAPO (HMPNs@BINAPO)。HMPNs@BINAPO 具有纳米级和球形形态，具有薄且介孔的壳，适合反应物和产物的快速传质。α,β-不饱和酮和苯甲醛与 HSiCl 3的不对称还原羟醛反应，HMPNs@BINAPO 显示出与均相 BINAPO 相当的良好至优异的催化性能以及良好的可重复使用性，而非对映选择性和对映选择性没有明显下降。
• 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.
• BOLDRINI, GIAN PAOLO;MANCINI, FABRIZIO;TAGLIAVINI, EMILIO;TROMBINI, CLAUD+, J. CHEM. SOC. CHEM. COMMUN.,(1990) N3, C. 1680-1681
  作者：BOLDRINI, GIAN PAOLO、MANCINI, FABRIZIO、TAGLIAVINI, EMILIO、TROMBINI, CLAUD+

  DOI：——

  日期：——