(3R,4S)-3,4-dimethylbutyrolactone | 110171-22-7

• 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: (3R,4S)-3,4-dimethylbutyrolactone
• 英文别名: 3-Methyl-4-pentanolide, (3R,4S)-；(4R,5S)-4,5-dimethyloxolan-2-one
• CAS: 110171-22-7
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: PXIPZIPSDBXFQR-UHNVWZDZSA-N

物化性质

• 沸点：
  206.3±8.0 °C(Predicted)
• 密度：
  0.981±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (3R,4S)-3,4-dimethylbutyrolactone 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以89%的产率得到(+/-)-3-methyl-1,4-pentanediol
  参考文献：
  名称：

  Synthesis of diastereo- and enantiomerically pure anti-3-methyl-1,4-pentanediol via lipase catalysed acylation

  摘要：

  Racemic trans-4,5-dimethylhydrofuran-2(3H)-one was synthesised from 5-methyl-furan-2(3H)-one, (alpha-angelica lactone). The key reaction in the synthesis was the 1,4-conjugate addition of an organocuprate to 5-methylfuran-2(5H)-one (beta-angelica lactone). Different types of organocuprates were tested with the highest anti:syn ratio of 99.4:0.6 being obtained by the use of a Gilman organocuprate reagent. The enantioselective acylation of racemic 3-methyl-pentan-1,4-diol, catalysed by a variety of lipases in organic media, was investigated. The highest enantioselectivity (E > 400) was obtained when Novozyme 435 was used as the catalyst at a water activity of a(w) similar to 0. Thus, both enantiomers, (3S,4R)- and (3R,4S)-3-methyl-pentan-1,4-diol, were obtained in very high diastereomeric (> 99% de) and enantiomeric purities (> 99.8% and > 97.4% ee, respectively). (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.01.043
• 作为产物：
  描述：

  (+/-)-3-methyl-1,4-pentanediol 在 NaOH buffer 、 horse liver alcohol dehydrogenase 、 β-烟酰胺腺嘌呤二核苷酸 、 聚甘氨酸 作用下， 反应 3.0h， 生成 (3R,4S)-3,4-dimethylbutyrolactone
  参考文献：
  名称：

  Synthesis of diastereo- and enantiomerically pure anti-3-methyl-1,4-pentanediol via lipase catalysed acylation

  摘要：

  Racemic trans-4,5-dimethylhydrofuran-2(3H)-one was synthesised from 5-methyl-furan-2(3H)-one, (alpha-angelica lactone). The key reaction in the synthesis was the 1,4-conjugate addition of an organocuprate to 5-methylfuran-2(5H)-one (beta-angelica lactone). Different types of organocuprates were tested with the highest anti:syn ratio of 99.4:0.6 being obtained by the use of a Gilman organocuprate reagent. The enantioselective acylation of racemic 3-methyl-pentan-1,4-diol, catalysed by a variety of lipases in organic media, was investigated. The highest enantioselectivity (E > 400) was obtained when Novozyme 435 was used as the catalyst at a water activity of a(w) similar to 0. Thus, both enantiomers, (3S,4R)- and (3R,4S)-3-methyl-pentan-1,4-diol, were obtained in very high diastereomeric (> 99% de) and enantiomeric purities (> 99.8% and > 97.4% ee, respectively). (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.01.043

文献信息

• Auto-protonation diastereoselective d' enolates issus de l'addition-1,4 d'nethiolates avec des enones
  作者：Sald Berrada、Stéphane Desert、Patrick Metzner

  DOI：10.1016/s0040-4020(01)85987-1

  日期：1988.1

  steps : Michael addition gives an elusive enolate which undergoes a fast “auto-protonation” : transfer of the hydrogen alpha to the thiocarbonyl group towards the enolate moiety. Geometry of the enethiolate double bond is unique and probably cis. An intramolecular concerted auto-protonation mechanism is discussed and a pseudo-cyclic transition state is tentatively assigned. An example of a tandem Michael

  锂化的二硫代乙酸甲酯与α，β-二取代的烯酮的1，4-加成反应得到非对映异构的5-氧代二硫代链烷酸酯。通过化学相关将顺式构型分配给主要的非对映异构体。用2,2,4-三甲基-4-己烯-3 1和2-亚乙基环链烷酮可获得很高的非对映选择性，使该反应可用于选择性合成具有1,2-相邻不对称碳的无环或半环链。立体风化过程与通常观察到的非环状非对映体烯酸酯质子化的过程相反（Houk模型）。诱捕实验表明，水解之前存在的物质不是烯醇盐而是烯硫醇盐，已经具有同构立体化学。这些Enefhiolates来自以下步骤：迈克尔加成反应产生难以捉摸的烯醇化物，该烯醇化物经历快速的“自动质子化”：氢α到硫代羰基的朝着烯醇化物部分的转移。烯硫醇双键的几何结构是独特的，可能是顺式的。讨论了分子内协调的自动质子化机制，并暂时分配了伪循环过渡态。串联迈克尔加成/克莱森重排的一个实例是通过将加成中间体进行S-烯丙基化，然后在室温下将
• New methods for reductive free-radical cyclizations of α-bromoacetals to 2-alkoxytetrahydrofurans with activated chromium(II)-acetate
  作者：Claus Hackmann、Hans J. Schäfer

  DOI：10.1016/s0040-4020(01)81285-0

  日期：1993.5

  free-radical cyclization of α-bromoacetals 4 to 2-alkoxytetrahydrofurans 5 in 54–93% yield induced by activated chromium(II)-acetate. Four new methods have been developed in order to activate the transition metal. Two of them require only catalytic amounts of chromium(II)-acetate, because it can be regenerated in situ chemically or electrochemically. The diastereoselectivity of the cyclization depends on

  描述了一种合成γ-丁内酯6的方法，其中关键步骤是将α-溴缩醛4自由基环化为2-烷氧基四氢呋喃5，这是由乙酸铬（II）活化引发的，产率为54-93％。为了激活过渡金属，已经开发了四种新方法。其中两个仅需要催化量的乙酸铬（II），因为它可以化学或电化学方式原位再生。环化的非对映选择性取决于4的取代模式，范围在30.4：1和1：54.8之间。
• Calcium(II)- and Triflimide-Catalyzed Intramolecular Hydroacyloxylation of Unactivated Alkenes in Hexafluoroisopropanol
  作者：Chenxiao Qi、Shengwen Yang、Vincent Gandon、David Lebœuf

  DOI：10.1021/acs.orglett.9b02705

  日期：2019.9.20

  hydroacyloxylation of unactivated alkenes, offering a streamlined access to relevant γ-lactones, which features the utilization of either a calcium(II) salt or triflimide as a catalyst in hexafluoroisopropanol. This method could be applied to the synthesis of natural products and the late-stage functionalization of natural and bioactive molecules. Additionally, DFT computations were used to elucidate the twist

  我们报告了未活化烯烃的有效分子内氢酰氧基化作用，提供了对相关γ-内酯的流线型通道，其特征在于利用了钙盐（II）或三氟甲酰亚胺作为六氟异丙醇中的催化剂。该方法可用于天然产物的合成以及天然和生物活性分子的后期功能化。此外，DFT计算用于阐明在未活化烯烃的加氢酰胺化和加氢酰氧基化之间有关5和6元环形成的反应性扭曲。
• On the Stereoselectivity of γ-Lactol Substitutions with Allyl- and Propargylsilanes − Synthesis of Disubstituted Tetrahydrofuran Derivatives
  作者：Andreas Schmitt、Hans-Ulrich Reißig

  DOI：10.1002/1099-0690(200012)2000:23<3893::aid-ejoc3893>3.0.co;2-e

  日期：2000.12

  Monosubstituted γ-lactols 1a−1c, 3a−3c and 4a−4c, as well as disubstituted γ-lactol 5 and the γ-hydroxy-substituted γ-lactone 6, were transformed into disubstituted tetrahydrofuran derivatives by treatment with allyl- and propargylsilanes in the presence of Lewis acids. The diastereoselectivities were moderate to excellent and are interpreted by application of the Felkin−Anh model to cyclic oxocarbenium

  单取代的 γ-乳醇 1a-1c、3a-3c 和 4a-4c，以及双取代的 γ-乳醇 5 和 γ-羟基取代的 γ-内酯 6，通过用烯丙基-和炔丙基硅烷处理转化为双取代的四氢呋喃衍生物。路易斯酸的存在。非对映选择性中等至极好，可以通过将 Felkin-Anh 模型应用于环状氧碳鎓离子来解释。讨论了中间体构象异构体之间平衡的影响。在此基础上可以解释 4-取代 γ-内酯 3 令人惊讶的高非对映选择性。
• Stereoselective Selenolactonization by Superelectrophilic Benzeneselenenyl Triflate
  作者：Shizuaki Murata、Toshiyasu Suzuki

  DOI：10.1246/cl.1987.849

  日期：1987.5.5

  Benzeneselenenyl triflate is prepared from benzeneselenenyl chloride and silver trifluoromethanesulfonate. It performs selenium-induced cyclization of β,γ-, γ,δ-, and δ,ε-unsaturated carboxylic acids.

  苯硒三氟甲磺酸酯是由苯硒氯化物和三氟甲磺酸银制备的。它能够促进β,γ-、γ,δ-和δ,ε-不饱和羧酸的硒诱导环化反应。