(R)-(+)-5-methyl-1-phenyl-1-hexyn-3-ol

• 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: (R)-(+)-5-methyl-1-phenyl-1-hexyn-3-ol
• 英文别名: 5-methyl-1-phenyl-1-hexyn-3-ol；(3R)-5-methyl-1-phenylhex-1-yn-3-ol
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: JDZJGOREBVGUNA-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  苯乙炔 、 异戊醛 在 indium(III) bromide 、 dicyclohexylmethylamine 、 (R)-1,1'-Bi-2-naphthol 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 以85%的产率得到(R)-(+)-5-methyl-1-phenyl-1-hexyn-3-ol
  参考文献：
  名称：

  In(III)/BINOL 络合物催化醛的不对称炔化

  摘要：

  描述了使用催化量的 In(III)/BINOL 对芳香族和脂肪族醛进行不对称炔化。由于铟 (III) 催化剂的“双功能特性”，两种底物的双重活化可实现广泛的底物通用性和高对映选择性（83 至 >99% ee）。

  DOI：

  10.1021/ja053946n

文献信息

• Chiral Macrocycle-Catalyzed Highly Enantioselective Phenylacetylene Addition to Aliphatic and Vinyl Aldehydes
  作者：Zi-Bo Li、Tian-Dong Liu、Lin Pu

  DOI：10.1021/jo070091j

  日期：2007.6.1

  The 1,1‘-binaphthyl macrocycle (S)-2 is found to be an excellent catalyst for the alkyne addition to aldehydes. In the presence of (S)-2 (20 mol %) and Me2Zn (2 equiv) in THF at room temperature, the addition of phenylacetylene to linear or branched aliphatic aldehydes and vinyl aldehydes gave various propargylic alcohols with 89−96% ee.

  发现1,1'-联萘大环（S）-2是炔烃加成醛的极佳催化剂。在室温下，在THF中存在（S）-2（20 mol％）和Me 2 Zn（2当量）的情况下，将苯乙炔添加到直链或支链脂族醛和乙烯基醛中，制得89-96％的各种炔丙醇ee。
• Synthesis of new β-hydroxy amide ligands and their Ti(IV) complex-catalyzed enantioselective alkynylation of aliphatic and vinyl aldehydes
  作者：Ya-Min Li、Yi-Quan Tang、Xin-Ping Hui、Lu-Ning Huang、Peng-Fei Xu

  DOI：10.1016/j.tet.2009.03.005

  日期：2009.5

  new chiral β-hydroxy amide ligands were synthesized via the reaction of benzyl chloride and amino alcohols derived from l-tyrosine. The titanium(IV) complex of chiral ligand 8b was found to be an effective catalyst for the asymmetric alkynylation of aliphatic, vinyl and aromatic aldehydes. The propargyl alcohols were obtained in highly enantiomeric excesses (up to 96% ee) under optimized conditions.

  通过苄基氯与衍生自1-酪氨酸的氨基醇的反应，合成了三个新的手性β-羟基酰胺配体。发现手性配体8b的钛（IV）配合物是脂族，乙烯基和芳族醛的不对称烷基化的有效催化剂。在优化条件下以高度对映体过量（最高达96％ee）获得炔丙醇。
• Enantioselective addition of phenylacetylene to aldehydes catalyzed by polymer-supported titanium(IV) complexes of β-hydroxy amides
  作者：Xin-Ping Hui、Lu-Ning Huang、Ya-Min Li、Ren-Lin Wang、Peng-Fei Xu

  DOI：10.1002/chir.20749

  日期：——

  A series of polymer‐supported chiral β‐hydroxy amides and C2‐symmetric β‐hydroxy amides have been synthesized and successfully used for the enantioselective addition of phenylacetylene to aldehydes. High yields (up to 93%) and enantioselectivities (up to 92% ee) were achieved by using polymer‐supported chiral β‐hydroxy amide 4b. The resin 4b is reused four times, giving the product with enantioselectivity

  合成了一系列聚合物支撑的手性β-羟基酰胺和C 2-对称β-羟基酰胺，并成功用于苯乙炔对醛的对映选择性加成。通过使用聚合物负载的手性β-羟基酰胺4b可以实现高收率（高达93％）和对映选择性（高达92％ee）。树脂4b重复使用四次，得到对映选择性为80％ee的产物。幸运的是，发现该杂多体系不仅适用于芳族醛，而且适用于脂族醛。《手性》，2010年。©2009 Wiley-Liss，Inc.。
• Studies on Pd(II)-Catalyzed Synthesis of (<i>Z</i>)-α-Haloalkylidene-β-lactones from Cyclocarbonylation of 2-Alkynols and the Subsequent Coupling Reactions
  作者：Shengming Ma、Bin Wu、Xuefeng Jiang、Shimin Zhao

  DOI：10.1021/jo0480038

  日期：2005.4.1

  A good regio- and stereoselectivity was observed for the PdCl2-catalyzed cyclocarbonylation of 2-alkynols with CuCl2 affording (Z)-alpha-chloroalkylidene-beta-lactons. The highly optically active (Z)-alpha-chloroalkylidene-beta-lactones could be easily prepared from the readily available optically active propargylic alcohols. The Pd(II)-catalyzed cyclocarbonylation of 2-alkynols with CuBr2 was also studied. Although the yields of (Z)-alpha-bromoalkylidene-beta-lactones were low, due to the relatively higher activity of the C-Br bond, the coupling reactions of (Z)-alpha-bromoalkylidene-beta-lactones were quite smooth to afford the corresponding products in high yields. A rationale for this reaction is discussed.
• Synthesis of new Schiff base-camphorsulfonyl amide ligands and in situ screening in the asymmetric additions of organozinc reagents to aldehydes
  作者：Jiangtao Sun、Xu Pan、Zhenya Dai、Chengjian Zhu

  DOI：10.1016/j.tetasy.2008.10.017

  日期：2008.11

  We have designed and synthesized a new library of highly modular Schiff base-camphorsulfonyl amide ligands from readily available starting materials. These ligands have been used in the asymmetric addition of diethyl zinc to aldehydes in good yields (up to 91%) and high enantioselectivities (up to 93%). Moreover, when the ligands were used in the asymmetric addition of phenylacetylene to aldehydes, good yields and moderate to high ee values (up to 90%) were obtained. The introduction of the camphorsulfonyl moiety into the ligands is highly critical for the selectivities of the reactions. Published by Elsevier Ltd.