(S)-4-hydroxy-5-hexenoic acid lactone | 91199-39-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (S)-4-hydroxy-5-hexenoic acid lactone
• 英文别名: (S)-4-vinyl butyrolactone；(S)-5-vinyldihydrofuran-2(3H)-one；(5S)-5-ethenyloxolan-2-one
• CAS: 91199-39-2
• 化学式: C₆H₈O₂
• 分子量: 112.128
• InChiKey: NUZVHQQEGICDQB-RXMQYKEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  sodium methylate 、 (S)-4-hydroxy-5-hexenoic acid lactone 在 甲醇 作用下， 反应 3.0h， 以100%的产率得到(S)-4-hydroxy-5-hexenoic acid methyl ester
  参考文献：
  名称：

  Homochiral 4-hydroxy-5-hexenoic acids and their derivatives and homologues from carbohydrates

  摘要：

  Efficient routes to chiral 4-hydroxy-5-hexenoic acids and lactones from D-gluconic acid-delta -lactone and L-mannonic acid-gamma -lactone are described. In this approach, the starting lactones are converted to 2,6-dibromo compounds that readily undergo zinc mediated elimination to generate the terminal alkene group in concert with 2-deoxygenation. The integrity of the remaining stereocenters is preserved during the reaction. The related important pharmaceutical intermediates (S)-3-hydroxy-4-pentenoic acid and (S)-1.3-dihydroxy-4-pentene were also prepared from 2-deoxyribose via the corresponding aldonolactone. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00053-2
• 作为产物：
  描述：

  葡萄糖酸内酯 在 copper(l) iodide 、 三甲基氯硅烷 、 氢溴酸 、 三正丁基氢锡 、 溶剂黄146 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (S)-4-hydroxy-5-hexenoic acid lactone
  参考文献：
  名称：

  Homochiral 4-hydroxy-5-hexenoic acids and their derivatives and homologues from carbohydrates

  摘要：

  Efficient routes to chiral 4-hydroxy-5-hexenoic acids and lactones from D-gluconic acid-delta -lactone and L-mannonic acid-gamma -lactone are described. In this approach, the starting lactones are converted to 2,6-dibromo compounds that readily undergo zinc mediated elimination to generate the terminal alkene group in concert with 2-deoxygenation. The integrity of the remaining stereocenters is preserved during the reaction. The related important pharmaceutical intermediates (S)-3-hydroxy-4-pentenoic acid and (S)-1.3-dihydroxy-4-pentene were also prepared from 2-deoxyribose via the corresponding aldonolactone. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00053-2

文献信息

• Total Synthesis of (18<i>S</i>)- and (18<i>R</i>)-Homolargazole by Rhodium-Catalyzed Hydrocarboxylation
  作者：Christoph Schotes、Dmytro Ostrovskyi、Johanna Senger、Karin Schmidtkunz、Manfred Jung、Bernhard Breit

  DOI：10.1002/chem.201303300

  日期：2014.2.17

  derivatives, in which the macrocycle of natural largazole is extended by one methylene group, were prepared by the recently developed rhodium‐catalyzed hydrocarboxylation reaction onto allenes. This strategy gives access to both the (18S)‐ and (18R)‐stereoisomers in high stereoselectivity under ligand control.

  通过最近开发的铑催化的加氢羰基化反应生成丙二烯，可以制备天然拉尔唑的大环延伸一个亚甲基的高拉莫拉唑衍生物。这种策略可以在配体控制下以高立体选择性获得（18 S）-和（18 R）-立体异构体。
• Enantioselective Allylic Hydroxylation of ω-Alkenoic Acids and Esters by P450 BM3 Monooxygenase
  作者：Katharina Neufeld、Birgit Henßen、Jörg Pietruszka

  DOI：10.1002/anie.201403537

  日期：2014.11.24

  allylic alcohols of ω‐alkenoic acids and derivatives thereof are highly important building blocks for the synthesis of biologically active compounds. The direct enantioselective CH oxidation of linear terminal olefins offers the shortest route toward these compounds, but known synthetic methods are limited and suffer from low selectivities. Described herein is an enzymatic approach using the P450

  ω-链烯酸的手性烯丙基醇及其衍生物是合成生物活性化合物的重要组成部分。直链末端烯烃的直接对映体CH氧化提供了通往这些化合物的最短途径，但是已知的合成方法受到限制，并且选择性低。本文介绍的是一种使用P450 BM3单加氧酶突变体A74G / L188Q的酶促方法，该酶催化具有高至极好的化学和对映选择性的烯丙基羟基化反应，从而提供所需的仲醇。
• Enantioselective Lactonization by π‐Acid‐Catalyzed Allylic Substitution: A Complement to π‐Allylmetal Chemistry
  作者：Arun Raj Kizhakkayil Mangadan、Ji Liu、Aaron Aponick

  DOI：10.1002/anie.202108336

  日期：2021.10.4

  Asymmetric allylic alkylation (AAA) is a powerful method for the formation of highly useful, non-racemic allylic compounds. Here we present a complementary enantioselective process that generates allylic lactones via π-acid catalysis. More specifically, a catalytic enantioselective dehydrative lactonization of allylic alcohols using a novel PdII-catalyst containing the imidazole-based P,N-ligand (S)-StackPhos

  不对称烯丙基烷基化 (AAA) 是形成非常有用的非外消旋烯丙基化合物的有效方法。在这里，我们提出了一种互补的对映选择性过程，该过程通过 π 酸催化生成烯丙内酯。更具体地说，报道了使用含有咪唑基P , N-配体 ( S )-StackPhos的新型 Pd II催化剂对烯丙醇进行催化对映选择性脱水内酯化。高产率反应操作简单，对映选择性高达 99 % ee. 该策略有助于用表面上更好的离去基团替换产品中的不良离去基团，避免因平衡外消旋化而引起的并发症。
• Intramolecular Tsuji–Trost-type Allylation of Carboxylic Acids: Asymmetric Synthesis of Highly π-Allyl Donative Lactones
  作者：Yusuke Suzuki、Tomoaki Seki、Shinji Tanaka、Masato Kitamura

  DOI：10.1021/jacs.5b05786

  日期：2015.8.5

  and low E factor. This success can be ascribed to the higher reactivity of allylic alcohols as compared with the allyl ester products in soft Ru/hard Brønstead acid combined catalysis, which can function under slightly acidic conditions unlike the traditional Pd-catalyzed system. Detailed analysis of the stereochemical outcome of the reaction using an enantiomerically enriched D-labeled substrate

  已经通过使用带有轴向手性吡啶甲酸型配体（Cl-Naph-PyCOOH：naph = 萘基，py = 吡啶）的阳离子 CpRu 络合物实现了 Tsuji-Trost 型羧酸的不对称烯丙基化。羧酸和烯丙醇通过释放水分子内缩合，而无需亲核试剂或亲电试剂部分的化学计量活化，从而实现高原子和步进经济性以及低 E 因子。这一成功可归因于烯丙醇与软 Ru/硬 Brønstead 酸联合催化中的烯丙酯产品相比具有更高的反应性，与传统的 Pd 催化体系不同，它可以在微酸性条件下发挥作用。
• LIGAND FOR ASYMMETRIC SYNTHESIS CATALYST, AND PROCESS FOR PRODUCTION OF ALPHA-ALKENYL CYCLIC COMPOUND USING SAME
  申请人：Kitamura Masato

  公开号：US20120220780A1

  公开（公告）日：2012-08-30

  Disclosed are: a ligand for an asymmetric synthesis catalyst; and a process for producing an α-alkenyl cyclic compound using the ligand. Specifically disclosed are: a ligand for an asymmetric synthesis catalyst, which is represented by any one of formulae (1) to (4) [wherein R 1 represents —Cl or —Br; R 2 represents —CH 3 or —CF 3 ; and R 3 represents —CH 2 —CH═CH 2 or —H]; and a process for producing an α-alkenyl cyclic compound using the ligand.

  公开了一种用于不对称合成催化剂的配体以及使用该配体制备α-烯丙基环状化合物的方法。具体公开了一种用于不对称合成催化剂的配体，其由公式（1）到（4）中的任一式所表示[其中R1代表—Cl或—Br；R2代表—CH3或—CF3；R3代表—CH2—CH═CH2或—H]，以及使用该配体制备α-烯丙基环状化合物的方法。