3,5-Ditert-butyl-2-[2-(hydroxymethyl)naphthalen-1-yl]phenol | 145497-48-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3,5-Ditert-butyl-2-[2-(hydroxymethyl)naphthalen-1-yl]phenol
• CAS: 145497-48-9
• 化学式: C₂₅H₃₀O₂
• 分子量: 362.512
• InChiKey: SMJCYAIWLHSLLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,5-Ditert-butyl-2-[2-(hydroxymethyl)naphthalen-1-yl]phenol 在 pyridinium chlorochromate 作用下， 以 四氢呋喃 为溶剂， 以83%的产率得到1-(4',6'-di-tert-butyl-2'-hydroxyphenyl)naphthalene-2-carbaldehyde
  参考文献：
  名称：

  Biaryl hydroxy aldehydes as intermediates in the metal-assisted atropo-enantioselective reduction of biaryl lactones: Structures and aldehyde-lactol equilibria

  摘要：

  The synthesis of substituted 1-(2'-hydroxyphenyl)naphthalene-2-carbaldehydes 4 and 6-alkoxy-6H-pyrans 7 and 8, analogs of the postulated metallated intermediates in the atropo-enantioselective ring cleavage of configuratively unstable biaryl lactones 2, is described. While the equilibria between the open hydroxy aldehydes 4 and the cyclic lactol structures 3 are completely shifted towards 4 for the derivatives 4c-g with substituents ortho to the biaryl axis, the lactol forms are the dominating structures (ca. 50-100%) for the ortho-unsubstituted compounds. For the lactols 3 and their acetalic analogs 6, 7, and 8, those diastereomeric conformations are preferred (77-100%) that have the exo-oxygen function axial. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00618-8
• 作为产物：
  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

文献信息

• The Atropo-Enantioselective Reduction of Configurationally Unstable Biaryl Hydroxy Aldehydes - A Novel Approach to Axially Chiral Biaryls
  作者：Gerhard Bringmann、Matthias Breuning

  DOI：10.1055/s-1998-1728

  日期：1998.6

  The oxazaborolidine-assisted atropo-enantioselective catecholborane reduction of configurationally unstable biaryl hydroxy aldehydes to axially chiral biaryl alcohols by (dynamic) kinetic resolution is achieved in enantiomeric ratios (er) of up to 92:8. Using the same chiral auxiliary, the M- or, optionally, the P-configurated atropisomer can be obtained in good er's - just by variation of the relative quantity of the achiral reductant. This hints at the existence of two competing reaction pathways with opposite asymmetric inductions. The enantiomeric ratios observed strongly depend on the relative steric demand of the substituents ortho to the biaryl axis.

  在噁唑硼烷辅助下，通过（动态）动力学解析将构型不稳定的双芳基羟基醛还原成轴向手性双芳基醇的邻苯二酚硼烷对映体选择性还原，对映体比（er）可达 92:8。使用相同的手性助剂，只需改变非手性还原剂的相对数量，就能以较好的对映体比（er's）获得 M-或 P-配置的异构体。这表明存在着两种具有相反不对称诱导作用的竞争反应途径。观察到的对映体比率在很大程度上取决于双芳基轴正向取代基的相对立体需求。
• 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
• 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：——
• ASYMMETRIC SYNTHESIS OF (M)-2-HYDROXYMETHYL-1-(2-HYDROXY-4,6-DIMETHYLPHENYL)NAPHTHALENE VIA A CONFIGURATIONALLY UNSTABLE BIARYL LACTONE
  作者：Bringmann, Gerhard、Breuning, Matthias、Henschel, Petra、Hinrichs, Jürgen、Greenen, Peter M.、Curran, Dennis P.

  DOI：10.15227/orgsyn.079.0072

  日期：——