3,4,4-trimethyl-1-phenylpent-1-yn-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: 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol
• 英文别名: (R)-3,4,4-trimethyl-1-phenylpent-1-yn-3-ol；(S)-3,4,4-trimethyl-1-phenyl-pent-1-yn-3-ol；(3S)-3,4,4-trimethyl-1-phenylpent-1-yn-3-ol
• 化学式: C₁₄H₁₈O
• 分子量: 202.296
• InChiKey: FNOTWYZKEJTYEO-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  频哪酮 、 苯乙炔 在 (R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine 、 Dimethylzinc 作用下， 以 甲苯 为溶剂， 反应 36.0h， 生成 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol 、 (R)-3,4,4-trimethyl-1-phenylpent-1-yn-3-ol
  参考文献：
  名称：

  Zn（salen）配合物催化的酮的对映选择性炔基化。

  摘要：

  DOI：

  10.1002/anie.200351230

文献信息

• Scope and Mechanistic Analysis of the Enantioselective Synthesis of Allenes by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic Rearrangement between Donor/Acceptor Carbenoids and Propargylic Alcohols
  作者：Zhanjie Li、Vyacheslav Boyarskikh、Jørn H. Hansen、Jochen Autschbach、Djamaladdin G. Musaev、Huw M. L. Davies

  DOI：10.1021/ja3061529

  日期：2012.9.19

  Rhodium-catalyzed reactions of tertiary propargylic alcohols with methyl aryl- and styryldiazoacetates result in tandem reactions, consisting of oxonium ylide formation followed by [2,3]-sigmatropic rearrangement. This process competes favorably with the standard O-H insertion reaction of carbenoids. The resulting allenes are produced with high enantioselectivity (88-98% ee) when the reaction is catalyzed by the

  炔丙基叔醇与甲基芳基乙酸酯和苯乙烯基重氮乙酸酯的铑催化反应导致串联反应，包括氧鎓叶立德形成，然后是 [2,3]-σ 重排。该过程与类卡宾的标准 OH 插入反应相得益彰。当反应由四脯氨酸二铑配合物 Rh(2)(S-DOSP)(4) 催化时，生成的丙二烯具有高对映选择性 (88-98% ee)。当外消旋叔炔丙醇用作底物时，可以进行动力学拆分。在动力学拆分条件下，形成的丙二烯具有良好的非对映选择性和对映选择性（高达6.1:1 dr，88-93% ee），未反应的醇被对映体富集到65-95% ee。计算研究表明，高不对称诱导是通过涉及两点连接的有组织的过渡态获得的：醇氧与类卡宾之间的叶立德形成以及醇与羧酸盐配体的氢键合。2,3-sigmatropic 重排通过 OH 键的初始裂解进行，生成具有紧密开壳单线态、三线态和闭壳单线态电子态的中间体。该中间体将具有显着的双自由基特征，这与供体/受体类卡宾和更高度官能化的炔丙醇有利于
• Rhodium-Catalyzed and Chiral Zinc Carboxylate-Assisted Allenylation of Benzamides via Kinetic Resolution
  作者：Ruxia Mao、Yanliang Zhao、Xiaohan Zhu、Fen Wang、Wei-Qiao Deng、Xingwei Li

  DOI：10.1021/acs.orglett.1c02398

  日期：2021.9.17

  In this work, kinetic resolution of tertiary propargyl alcohols as an allenylating reagent has been realized via rhodium(III)-catalyzed C–H allenylation of benzamides. The reaction proceeded efficiently under mild conditions, and both the allenylated products and the propargyl alcohols were obtained in high enantioselectivities with an s-factor of up to 139. The resolution results from bias of the

  对映体富集的丙二烯是重要的组成部分。虽然它们已通过其他偶联方法获得，但很少通过 C-H 活化获得对映体富集的丙二烯。在这项工作中，通过铑（III）催化的苯甲酰胺的 C-H 烯丙基化实现了叔炔丙醇作为烯丙基化试剂的动力学拆分。该反应在温和的条件下有效进行，并以高对映选择性获得了s因子高达 139的烯丙基化产物和炔丙醇。分辨率来自两个炔丙基取代基的偏向性，并由手性羧酸锌辅助添加剂。
• 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。
• PHOSPHOROAMIDE COMPOUND, METHOD FOR PRODUCING THE SAME, LIGAND, COMPLEX, CATALYST, AND METHOD FOR PRODUCING OPTICALLY ACTIVE ALCOHOL
  申请人：National University Corporation Nagoya University

  公开号：EP2128167A1

  公开（公告）日：2009-12-02

  Disclosed is a method for highly efficiently obtaining an optically active alcohol from a carbonyl compound highly enantioselectively. Also disclosed is a ligand used in such a method. Specifically, an optically active alcohol is obtained by reacting a carbonyl compound and an organozinc compound by using a ligand (L) shown below.

  本发明公开了一种从羰基化合物中高效对映选择性地获得光学活性醇的方法。还公开了一种用于这种方法的配体。具体地说，通过使用下图所示的配体（L），使羰基化合物和有机锌化合物反应，得到光学活性醇。
• 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.