(R)-2-(4-fluorophenyl)-4-phenyl-but-3-yn-2-ol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (R)-2-(4-fluorophenyl)-4-phenyl-but-3-yn-2-ol
• 英文别名: 2-(4-fluorophenyl)-4-phenylbut-3-yn-2-ol；(2R)-2-(4-fluorophenyl)-4-phenylbut-3-yn-2-ol
• 化学式: C₁₆H₁₃FO
• 分子量: 240.277
• InChiKey: YSGHMIKHHBRHOY-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-氟苯乙酮 、 苯乙炔 在 titanium(IV) isopropylate benzene-1,3-bis-[(S)-SO₂NH-C(Bn)-C(Et)2-OH] 、 diethylzinc 作用下， 以 甲苯 为溶剂， 反应 121.0h， 生成 (S)-(-)-2-(4-fluorophenyl)-4-phenylbut-3-yn-2-ol 、 (R)-2-(4-fluorophenyl)-4-phenyl-but-3-yn-2-ol
  参考文献：
  名称：

  新的C 2-对称的双磺酰胺配体的合成及其在炔醛与醛和酮的对映选择性加成中的应用

  摘要：

  新颖的C 2-对称双磺酰胺配体易于通过三个简单步骤制备，并用于炔基锌试剂对醛的对映选择性加成。发现化合物7a是该反应的杰出配体。当使用4mol％的7a的催化剂负载量时，在非常温和的条件下获得了ee值高达97％的高对映选择性。当配体7a的量降低至2mol％时，仍达到高达95％ee的优异对映体控制水平。迄今为止，已开发出最经济的催化剂体系，用于在配体负载和对映选择性方面向芳族醛中添加末端炔烃。此外，配体7a发现与Ti（O - Pr）4组合可以有效地促进炔基锌试剂在非常温和的条件下与未活化的简单酮的加成反应。得到相应的手性叔炔丙醇，其对映体过量最高为81％。

  DOI：

  10.1002/adsc.200505162

文献信息

• Highly Enantioselective Addition of Phenylacetylene to Ketones Catalyzed by Bis(hydroxycamphorsulfonamide)-Copper(II) Complex
  作者：Rui Wang、Lei Liu、Yong-Feng Kang、Hua-Qing Cai、Chao Chen

  DOI：10.1055/s-2006-932473

  日期：——

  A chiral copper complex, generated from a C 2-sym­metric bis(hydroxycamphorsulfonamide) ligand (8 mol%) and Cu(OTf)2, has been discovered to effect high enantioselectivities in the addition of alkynylzinc to a series of simple ketones. The alkynylation of a variety of aromatic and aliphatic ketones resulted in excellent yields and enantioselectivities (83-98% ee). Even when the loadings of the catalyst is 5 mol%, up to 94% ee was obtained.

  一种由C2对称的双(羟基樟脑磺酰胺)配体(8摩尔%)和Cu(OTf)2生成的手性铜配合物，已被发现能显著提高烷炔基锌对一系列简单酮加成反应的立体选择性。对各种芳香族和脂肪族酮的炔基化反应，产率极高且具有优良的立体选择性(83-98% 对映体过量)。即使催化剂用量降至5摩尔%，也能获得高达94%的对映体过量。
• Enantioselective alkynylation of carbonyl compounds with trimethoxysilylalkynes catalyzed by lithium binaphtholate
  作者：Tomohiro Ueda、Kana Tanaka、Tomonori Ichibakase、Yuya Orito、Makoto Nakajima

  DOI：10.1016/j.tet.2010.07.080

  日期：2010.9

  Enantioselective alkynylation of aldehydes and ketones was accomplished using trimethoxysilylalkynes as alkynylating reagents and lithium 3,3′-diphenylbinaphtholate as a catalyst. Optically active propargylic alcohols were obtained in good to high chemical yields and enantioselectivities. Alkynylation of acetylpyridines afforded biologically active pyridyl propargylic alcohols in good enantioselectivities

  使用三甲氧基甲硅烷基炔烃作为炔基化试剂和3,3'-二苯基联萘甲酸锂实现对醛和酮的对映选择性炔基化。以良好至高的化学产率和对映选择性获得了光学活性的炔丙醇。乙酰吡啶的炔基化得到具有良好对映选择性的生物活性吡啶基炔丙基醇。
• Catalytic asymmetric addition of alkynylzinc reagents to ketones using polymer-supported chiral Schiff-base amino alcohols
  作者：Chao Chen、Liang Hong、Bangzhi Zhang、Rui Wang

  DOI：10.1016/j.tetasy.2007.11.040

  日期：2008.2

  Polymer-supported Schiff-base of optically active amino alcohols was used as chiral ligands in the enantioselective addition of alkynylzinc to simple ketones. At a 10 mol % ligand loading, chiral propargylic alcohols with moderate to good ee values (up to 89%) were produced. The polymeric catalyst could be recycled many times and used for further reactions.

  聚合物支撑的光学活性氨基醇的席夫碱用作手性配体，用于将炔基锌对映选择性加成至简单的酮中。在配体负载量为10 mol％的情况下，生产出具有中等至良好ee值（最高89％）的手性炔丙醇。聚合物催化剂可以循环多次并用于进一步的反应。
• Enantioselective Alkynylation of Aromatic Ketones Catalyzed by New Chiral Oxazolidine Ligands
  作者：Yong-Feng Kang、Lei Liu、Rui Wang、Yi-Feng Zhou、Wen-Jin Yan

  DOI：10.1002/adsc.200404278

  日期：2005.2

  New chiral oxazolidine ligands have been derived conveniently from natural amino acids in good yields. Their use in the enantioselective addition of phenylacetylene to aromatic ketones has been tested with the best ee being up to 88%. We provide a simple, practical and inexpensive method to generate chiral tertiary propargylic alcohols.

  新的手性恶唑烷配体已方便地从天然氨基酸中以高收率得到。已经测试了它们在将苯乙炔对映选择性加成到芳族酮中的用途，最佳ee高达88％。我们提供了一种简单，实用和廉价的方法来生成手性叔炔丙醇。
• Enantioselective alkynylation of ketones with trimethoxysilylalkynes using lithium binaphtholate as a catalyst
  作者：Kana Tanaka、Tomohiro Ueda、Tomonori Ichibakase、Makoto Nakajima

  DOI：10.1016/j.tetlet.2010.02.084

  日期：2010.4

  Chiral lithium 3,3'-diphenylbinaphtholate successfully catalyzed the alkynylation of ketone with trimethoxysilylalkyne, affording chiral tertiary propargylic alcohols in high chemical yields and high enantioselectivities. The present reaction could be extended to the alkynylation of acetylpyridine, which afforded a biologically active pyridyl propargylic alcohol in good enantioselectivity. (c) 2010 Elsevier Ltd. All rights reserved.