(2R*,3S*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione | 73893-85-3

• 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: (2R*,3S*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione
• 英文别名: maso-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；meso-2,3-dimethyl-1,4-diphenylbutane-1,4-dione；meso-2,3-dimethyl-1,4-diphenyl-1,4-butandione；(2R,3S)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione
• CAS: 73893-85-3
• 化学式: C₁₈H₁₈O₂
• 分子量: 266.34
• InChiKey: HBYWOMLOWVKVBT-OKILXGFUSA-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：

  (2R*,3S*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione 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：

  2-溴苯丙酮 在 sodium methylate 作用下， 以 四氢呋喃 为溶剂， 生成 (2R*,3S*)-2,3-dimethyl-1,4-diphenylbutane-1,4-dione
  参考文献：
  名称：

  3,6-二芳基-2,6-辛二烯和2,5-二芳基-3,4-二甲基-1,5-己二烯的光诱导电子转移应付重排：立体特异性和双环[2.2.0]的意外形成。己烷衍生物。

  摘要：

  在9,10-二氰基蒽敏感的光致电子转移条件下，（Z，Z）-，（E，E）-，（E，Z）-3,6-diaryl-2,6-octadiene和（d， 1），（内消旋）-2，5-二芳基-3，4-二甲基-1，5-己二烯立体定向地进行Cope重排，得到Cope光固定混合物。值得注意的是，4-甲基苯基衍生物的光诱导电子转移Cope重排与顺式或内式顺-1,4-双（4-甲基苯基）-2,3-二甲基双环[2.2.0]己烷的形成同时发生在应付光致静止混合物中。观察到的Cope重排的立体特异性和双环[2.2.0]己烷衍生物的形成证明了椅子和船用1,4-二芳基-1,2-二甲基环己烷-1,4-二基和阳离子自由基中间体的中间体应对重排周期。反式和反式，顺-1,4-二芳基-5，6-二甲基-2,3-二氮杂双环[2.2.2]辛-2-烯进一步支持二甲醚中间体在Cope重排循环中的干预。通过光声分析，提出了一种阳离子自由基环化-双

  DOI：

  10.1021/jo981775h

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。
• Oxovanadium(v)-induced diastereoselective oxidative homocoupling of boron enolates
  作者：Toru Amaya、Takaya Masuda、Yusuke Maegawa、Toshikazu Hirao

  DOI：10.1039/c3cc49624d

  日期：——

  Oxovanadium(v)-induced dl-selective oxidative coupling of (Z)-boron enolate was demonstrated to give the corresponding 2,3-disubstituted 1,4-diketone in a good yield. High selectivity (up to 94 : 6) was attained when the reaction was performed with VO(OPr-i)2Cl at -30 degrees C.

  氧杂钒（v）诱导的（Z）-硼烯醇化物的dl-选择性​​氧化偶联被证明以良好的产率得到了相应的2,3-二取代的1,4-二酮。当与VO（OPr-i）2Cl在-30摄氏度下进行反应时，可获得高选择性（高达94：6）。
• 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。
• Diastereo- and Enantioselective Synthesis of<i>syn</i>-2,3-Disubstituted 1,4-Diketones<i>via</i>Oxidative Coupling of Metalated Hydrazones
  作者：Dieter Enders、Peter Müller、Daniela Klein

  DOI：10.1055/s-1998-1562

  日期：1998.1

  An efficient diastereo- and enantioselective synthesis of syn-2,3-disubstituted 1,4-diketones 4 is described. Key step of the procedure is the oxidative coupling of the metalated SAMP/RAMP-hydrazones 2 with iodine, followed by oxidative cleavage of the dimerized bishydrazones 3 with ozone and subsequent separation of the minor meso-isomer by chromatography. The d,l-isomers of the title 1,4-diketones 4 are obtained in good overall yields (20-64%) and high diastereo- and enantiomeric excesses (de ≥ 98%, ee = 80- ≥ 95%).

  本文描述了syn-2,3-二取代-1,4-二酮4的高效对映选择性和非对映选择性合成方法。该过程的关键步骤是金属化的SAMP/RAMP脒2与碘的氧化耦合反应，随后用臭氧氧化断开二聚的双脒3，并通过色谱法分离出次要的内消旋异构体。标题1,4-二酮4的d,l异构体以良好的总收率（20-64%）和高度的非对映选择性及对映体过量（de ≥ 98%，ee = 80- ≥ 95%）获得。
• 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。