dl-2,3-dimethyl-1,4-diphenyl-1,4-butandione

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 二苄基丁烷木脂素
• 英文名称: dl-2,3-dimethyl-1,4-diphenyl-1,4-butandione
• 英文别名: (2S*,3S*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；rac-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；(2R*,3R*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；(2RS,3RS)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；(2S,3S)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione
• 化学式: C₁₈H₁₈O₂
• 分子量: 266.34
• InChiKey: HBYWOMLOWVKVBT-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dl-2,3-dimethyl-1,4-diphenyl-1,4-butandione 在 盐酸 作用下， 以 甲醇 、 氯仿 为溶剂， 生成 3,4-Dimethyl-2,5-diphenylfuran
  参考文献：
  名称：

  Intermediates in the Paal-Knorr Synthesis of Furans

  摘要：

  New experimental evidence for the mechanism of the Paal-Knorr reaction involving the acid-catalyzed cyclization of a 1,4-diketone to form a furan is reported. In aqueous or alcoholic solutions containing hydrochloric acid and in chloroform containing boron trifluoride-etherate d,l- and meso-3,4-diethyl-2,5-hexanediones (2r and 2m) cyclize at unequal rates; the stereochemical configuration of the unchanged done is preserved during the reaction. This disagrees with the commonly accepted mechanism involving the ring closure of the rapidly formed monoenol (11b) followed by loss of water. A pathway involving the rapid protonation of one of the carbonyls followed by the electrophilic attack on the protonated carbonyl by the enol being formed at the other carbonyl group (10c) is proposed to account for the difference in reaction rates between the diastereomers of 3,4-disubstituted 2,5-hexanediones (1-3). The following results also seem to support the intermediacy of 10c. The presence of two isopropyl groups in 3,4-diisopropyl-2,5-hexanedione (3) considerably reduces the rate of cyclization, The catalytic constants k(H)(+) for the cyclization of 2r and 2m are larger than the constants for enolization of methyl ketones. The diastereomers of 2,3-dimethyl-and 2,3-diethyl-1,4-diphenyl-1,4-butanediones (4 and 5), which could enolize only toward the center of the molecule, also react at different rates. The d,l and meso dideuterio analogs (d(2)-4r and d(2)-4m) exhibit a primary isotope effect during cyclization. The order of cyclization of 1,4-diphenyl-1,4-butanedione (6) and its analogs (7-9) reveals that the presence of electron-donating groups facilitate the reaction.

  DOI：

  10.1021/jo00107a006
• 作为产物：
  描述：

  (E)-2-phenyl-1-nitroprop-1-ene 在 oxonium 作用下， 以 水 为溶剂， 反应 8.0h， 生成 dl-2,3-dimethyl-1,4-diphenyl-1,4-butandione
  参考文献：
  名称：

  Highly diastereoselective synthesis of cyclic nitronic esters from 1-(4-morpholinyl)-1-phenylpropene with nitroolefins

  摘要：

  DOI：

  10.1016/s0040-4020(01)80071-5

文献信息

• Bioinspired total synthesis of tetrahydrofuran lignans by tandem nucleophilic addition/redox isomerization/oxidative coupling and cycloetherification reactions as key steps
  作者：Pratap R. Jagtap、Ivana Císařová、Ullrich Jahn

  DOI：10.1039/c7ob02848b

  日期：——

  A very short three-step approach to trans,trans,trans-2,5-diaryl-3,4-dimethyltetrahydrofuran lignans is reported. The carbon skeleton is assembled in a single step based on an unprecedented tandem reaction consisting of 1,2-addition of aryllithium reagents to α,β-unsaturated aldehydes, ruthenium-catalyzed redox isomerization of the resulting alkoxides to enolates and their dimerization triggered by

  据报道，反式，反式，反式-2,5-二芳基-3,4-二甲基四氢呋喃木脂素的非常短的三步法。碳骨架是基于空前的串联反应由一个步骤组装而成的，该串联反应由芳基锂试剂与α，β-不饱和醛的1,2-加成反应，钌催化的所得醇盐氧化还原异构化为烯醇化物以及它们的二聚反应引发。电子氧化。形成的2，3-二烷基-1，4-二酮具有中等至良好的d / l-非对映选择性，并通过还原和非对映选择性环醚化转化为目标四氢呋喃木脂素。
• Electrochemical and Photocatalytic Oxidative Coupling of Ketones via Silyl Bis-enol Ethers
  作者：Aidan C. Caravana、Benjamin Nagasing、Sandeep Dhanju、Rebekah G. Reynolds、Emily A. Weiss、Regan J. Thomson

  DOI：10.1021/acs.joc.1c00384

  日期：2021.5.7

  Diastereoselective oxidative coupling of ketones through a silyl bis-enol ether intermediate by anodic and photocatalytic oxidation is reported. These methods provide several 1,4-diketones in good yields without the need for stoichiometric metal oxidants. The strategic use of a silicon tether enables the coupling of both aromatic and aliphatic ketones as well as the synthesis of quaternary centers

  报道了通过阳极和光催化氧化通过甲硅烷基双烯醇醚中间体进行酮的非对映选择性氧化偶联。这些方法以良好的收率提供了几种 1,4-二酮，而不需要化学计量的金属氧化剂。硅系链的策略性使用使得芳香族和脂肪族酮的偶联以及四元中心的合成成为可能。循环伏安法用于深入了解反应的氧化事件。
• General and Efficient α-Oxygenation of Carbonyl Compounds by TEMPO Induced by Single-Electron-Transfer Oxidation of Their Enolates
  作者：Emanuela Dinca、Philip Hartmann、Jakub Smrček、Ina Dix、Peter G. Jones、Ullrich Jahn

  DOI：10.1002/ejoc.201200736

  日期：2012.8

  for the synthesis of protected α-oxygenated carbonyl compounds is reported. It is based on the single-electron-transfer oxidation of easily generated enolates to the corresponding α-carbonyl radicals. Coupling with the stable free radical TEMPO provides α-(piperidinyloxy) ketones, esters, amides, acids or nitriles in moderate-to-excellent yields. Enolate aggregates influence the outcome of the oxygenation

  报道了一种普遍适用的合成受保护的 α-氧化羰基化合物的方法。它基于将容易生成的烯醇化物单电子转移氧化为相应的 α-羰基自由基。与稳定的自由基 TEMPO 结合以中等至优异的产率提供 α-(哌啶基氧基) 酮、酯、酰胺、酸或腈。烯醇化物聚集体显着影响氧化反应的结果。对竞争反应进行了分析，并提出了将其最小化的条件。产物的化学选择性还原导致 N-O 键裂解为 α-羟基羰基化合物或羰基官能团还原为单保护的 1,2-二醇或 O-保护的氨基醇。
• Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones
  作者：Keshaba N Parida、Gulab K Pathe、Shimon Maksymenko、Alex M Szpilman

  DOI：10.3762/bjoc.14.84

  日期：——

  Due to their closely matched reactivity, the coupling of two dissimilar ketone enolates to form a 1,4-diketone remains a challenge in organic synthesis. We herein report that umpolung of a ketone trimethylsilyl enol ether (1 equiv) to form a discrete enolonium species, followed by addition of as little as 1.2-1.4 equivalents of a second trimethylsilyl enol ether, provides an attractive solution to

  由于它们紧密匹配的反应性，两个不同的酮烯醇酸酯的偶联形成1，4-二酮仍然是有机合成中的挑战。我们在本文中报道酮三酮甲硅烷基烯醇醚（1当量）的形成形成离散的烯醇，随后加入低至1.2-1.4当量的第二三甲基甲硅烷基烯醇醚，为该问题提供了有吸引力的解决方案。可以使用各种各样的烯醇化物以1％至38％至74％的产率形成1，4-二酮产物。由于使用了两种TMS烯醇醚作为前体，因此交叉偶联的优化应包括研究添加顺序。
• α-Arylation of ketones by aryllead triacetates. Effect of methyl and phenyl substitution at the α position
  作者：Jacqueline Morgan、John T. Pinhey、Bruce A. Rowe

  DOI：10.1039/a607543f

  日期：——

  An examination of the α-arylation of a number of ketones and their enolate salts by p-methoxyphenyllead triacetate provides further evidence for a very marked selectivity in the arylation reaction. It is found that the reaction proceeds well at tertiary α-carbons and at secondary centres activated by the presence of a phenyl group, but fails where the secondary centre is unactivated and at primary α-carbons.

  对多种酮及其烯醇盐与对甲氧基苯基三乙酸铅的α-芳基化反应的研究提供了进一步的证据，表明该芳基化反应具有显著的选择性。研究发现，该反应在三级α-碳位和受到苯基取代所激活的二级中心进行良好，但在未被激活的二级中心和一级α-碳位时则失败。