(M,S)-menthyl 1-(2,4-di-tert-butyl-6-hydroxyphenyl)-2-naphthoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (M,S)-menthyl 1-(2,4-di-tert-butyl-6-hydroxyphenyl)-2-naphthoate
• 英文别名: (P,S)-menthyl 1-(2,4-di-tert-butyl-6-hydroxyphenyl)-2-naphthoate；[(1S,2R,5S)-5-methyl-2-propan-2-ylcyclohexyl] 1-(2,4-ditert-butyl-6-hydroxyphenyl)naphthalene-2-carboxylate
• 化学式: C₃₅H₄₆O₃
• 分子量: 514.748
• InChiKey: LTVGKIBYHVEBTC-KIYFCNKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.1
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (M,S)-menthyl 1-(2,4-di-tert-butyl-6-hydroxyphenyl)-2-naphthoate 在 4-二甲氨基吡啶 、 草酰氯 、 potassium tert-butylate 、 水 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 26.5h， 生成 (M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one
  参考文献：
  名称：

  Atropisomerization Barriers of Configurationally Unstable Biaryl Compounds, Useful Substrates for Atroposelective Conversions to Axially Chiral Biaryls

  摘要：

  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.

  DOI：

  10.1021/jo9913356
• 作为产物：
  描述：

  D-薄荷醇 、 (M)-1,4-di-tert-butyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one 在 正丁基锂 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 168.0h， 以46%的产率得到(M,S)-menthyl 1-(2,4-di-tert-butyl-6-hydroxyphenyl)-2-naphthoate
  参考文献：
  名称：

  Atropisomerization Barriers of Configurationally Unstable Biaryl Compounds, Useful Substrates for Atroposelective Conversions to Axially Chiral Biaryls

  摘要：

  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.

  DOI：

  10.1021/jo9913356

文献信息

• 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.