(M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one | 138435-75-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: (M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one
• 英文别名: (P)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；1,3-di-tert -butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；1,3-di-tert-butyl-6H-benzo[b]naphtho[1,2d]pyranon-6-one；1,3-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；6H-Benzo[b]naphtho[1,2-d]pyran-6-one, 1,3-bis(1,1-dimethylethyl)-；1,3-ditert-butylnaphtho[2,1-c]chromen-6-one
• CAS: 138435-75-3；260061-18-5；260061-19-6
• 化学式: C₂₅H₂₆O₂
• 分子量: 358.48
• InChiKey: CWJFTBXWDZAALY-UHFFFAOYSA-N

物化性质

• 熔点：
  106-107 °C
• 沸点：
  486.7±35.0 °C(Predicted)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 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：

  (M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one 在 硼烷四氢呋喃络合物 、 (S)-2-甲基-CBS-恶唑硼烷 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 30.0 ℃ 、100.0 Pa 条件下， 反应 2.0h， 以99%的产率得到
  参考文献：
  名称：

  ASYMMETRIC SYNTHESIS OF (M)-2-HYDROXYMETHYL-1-(2-HYDROXY-4,6-DIMETHYLPHENYL)NAPHTHALENE VIA A CONFIGURATIONALLY UNSTABLE BIARYL LACTONE

  摘要：

  DOI：

  10.15227/orgsyn.079.0072
• 作为产物：
  描述：

  3,5-二叔丁基苯酚 在 bis-triphenylphosphine-palladium(II) chloride 4-二甲氨基吡啶 、 草酰氯 、 sodium acetate 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 6.0h， 生成 (M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one
  参考文献：
  名称：

  Bringmann, Gerhard; Hartung, Thomas; Goebel, Lothar, Liebigs Annalen der Chemie, 1992, # 3, p. 225 - 232

  摘要：

  DOI：

文献信息

• Extraordinary Microwave Effect on <i>atropo</i>-Enantioselective Catalytic Reduction of Biaryl Lactones
  作者：Kazuya Nushiro、Satoshi Kikuchi、Tohru Yamada

  DOI：10.1246/cl.2013.165

  日期：2013.2.5

  It was found that microwave irradiation under strictly controlled temperature conditions drastically enhanced the catalytic atropo-enantioselective Corey–Bakshi–Shibata (CBS) reduction of biaryl la...

  研究发现，在严格控制的温度条件下，微波辐射极大地增强了对联芳基 la 的催化 atropo-对映选择性 Corey-Bakshi-Shibata (CBS) 还原。
• Nondynamic Kinetic Resolution of Configurationally Stable Biaryl Lactones by Reduction with Oxazaborolidine-Activated Borane:  AM1 Studies and Experimental Verification
  作者：Gerhard Bringmann、Jürgen Hinrichs、Jürgen Kraus、Andreas Wuzik、Tanja Schulz

  DOI：10.1021/jo991729x

  日期：2000.4.1

  The complete mechanistic course of the atroposelective ring opening of a lactone-bridged biaryl, dinaphth[2,1-c:1',2'-e]oxepin-3-(5H)-one (3), with a chiral oxazaborolidine-BH3 complex was calculated using the semiempirical AM1 method. The first hydride transfer to the activated carbonyl function of the adduct complexes was elaborated to be the selectivity-determining step in the postulated five-step

  内酯桥联的芳基，萘并[2,1-c：1'，2'-e] oxepin-3-（5H）-一（3）与手性恶唑硼烷-的对位选择性开环的完整机理使用半经验AM1方法计算BH3配合物。在假定的五步机理中，首次氢化物转移到加合物配合物的活化羰基官能团上被精心设计为决定选择性的步骤。对映选择性的计算结果与实验结果吻合良好，因此对空间受阻且结构稳定的六元联芳基内酯1,3-二叔丁基-6H的对映选择性开环进行了相关计算。 -苯并[b]萘并[1,2-d]吡喃-6-一（6f）。这些计算预测（f）选择性会高度降低6f（在-78摄氏度下kM / kP = 358），通过分子内联芳基偶联以高收率顺利制备6f后，经实验充分证实（在-78摄氏度下kM / kP> 200）。在反应开始时，以与相应醇（M）-7f相同的对映体过量分离中间体羟基醛（M）-14最终显示了第一步氢化物转移步骤，以确定该方法的选择性。通过计算预测值和实验确认
• 1,3-Di-terf-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-thione, a Severely Helically Distorted Thionolactone-Bridged Biaryl
  作者：Gerhard Bringmann、Andreas Wuzik、Olaf Schupp、Karl Peters、Eva-Maria Peters

  DOI：10.1515/znb-1997-0310

  日期：1997.3.1

  The title compound 2c, a potentially useful synthetic intermediate in stereoselective biaryl synthesis, has been prepared from the oxolactone 1c, by treatment with Lawesson′s reagent. An X-ray structure analysis reveals its strongly helically distorted structure, the overall molecular distortion even slightly exceeding that of the corresponding oxo compound 1c.

  摘要：本文报道了一种可能有用的合成中间体2c，该中间体可用于立体选择性双芳基合成，该中间体是通过使用Lawesson's试剂处理氧杂内酯1c而制备的。X射线结构分析显示其强烈的螺旋畸变结构，整个分子畸变程度甚至略高于相应的氧代化合物1c。
• Atropisomerization Barriers of Configurationally Unstable Biaryl Compounds, Useful Substrates for Atroposelective Conversions to Axially Chiral Biaryls
  作者：Gerhard Bringmann、Markus Heubes、Matthias Breuning、Lothar Göbel、Michael Ochse、Bernd Schöner、Olaf Schupp

  DOI：10.1021/jo9913356

  日期：2000.2.1

  Configurationally unstable biaryl lactones of type (M)-1 reversible arrow (P)-1 and ring-opened 2-acyl-2'-hydroxy biaryl compounds of type (M)-4 reversible arrow (P)-4 are versatile precursors for the atroposelective preparation of axially chiral biaryls. The activation barriers of their atropisomerization process, which constitutes a fundamental precondition for the dynamic kinetic resolution, were determined by dynamic NMR spectroscopy for rapid processes and by HPLC-monitored racemization of enantiomerically enriched material for smaller interconversion rates. For the lactones, the free activation energies Delta G(298)(double dagger) increase with the steric demand of the substituent R ortho to the biaryl axis in the series H < OMe (t(1/2) approximate to ms) < Me (t(1/2) approximate to s) < Et < i-Pr (t(1/2) approximate to min) < t-Bu (t(1/2) approximate to d). The formally ring-opened 2-acyl-2'-hydroxy biaryls, which interconvert via the lactol isomers 5 as the cyclic (and thus configurationally less stable) intermediates, have a significantly slower atropisomerization rate as a result of the high loss in activation entropy Delta S-double dagger as a consequence of the required intermediate ring closure 4 --> 5.
• Bringmann, Gerhard; Hartung, Thomas; Goebel, Lothar, Liebigs Annalen der Chemie, 1992, # 7, p. 769 - 776
  作者：Bringmann, Gerhard、Hartung, Thomas、Goebel, Lothar、Schupp, Olaf、Peters, Karl、Schnering, Hans Georg von

  DOI：——

  日期：——