(M)-4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one | 214069-32-6

• 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)-4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one
• 英文别名: (P)-4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one；1-Methyl-4-propan-2-ylnaphtho[2,1-c]chromen-6-one
• CAS: 214069-32-6
• 化学式: C₂₁H₁₈O₂
• 分子量: 302.373
• InChiKey: MQDMQTPVIASXRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 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)-4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one 在 manganese(IV) oxide 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成 1-(2'-hydroxy3'-isopropyl-6'-methylphenyl)naphthalene-2-carbaldehyde
  参考文献：
  名称：

  钌催化还原胺化和动态动力学拆分轴向联芳基的对苯二酚选择性合成

  摘要：

  描述了通过级联转移氢化和动态动力学拆分策略，空前的钌催化的烷基胺对醛的对苯二酸选择性还原胺化反应。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高至高收率和高至优异的对映选择性快速组装轴向手性联芳基。另外，这样的结构基序可以作为手性配体或催化剂在对映选择性催化中具有潜在的应用。

  DOI：

  10.1021/acs.orglett.8b02785
• 作为产物：
  描述：

  1-bromo-2-(dibromomethyl)naphthalene 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 sodium acetate 、 palladium diacetate 、 silver nitrate 、 N,N-二甲基甲酰胺 、 三苯基膦 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 水 、 叔丁醇 为溶剂， 反应 50.25h， 生成 (M)-4-isopropyl-1-methyl-6H-benzo[b]naphtho[1,2-d]pyran-6-one
  参考文献：
  名称：

  借氢和动力学动力学拆分联芳基化合物的对映体选择性氧化还原中性胺化反应

  摘要：

  我们在此报告了一种新颖的对芳基化合物的新型对苯二酚选择性氧化还原中性胺化反应，该反应是由手性铱配合物和非手性布朗斯台德酸的协同催化下的借入氢和动态动力学拆分级联触发的。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高至高收率和高至优异的对映选择性快速组装轴向手性联芳基化合物。

  DOI：

  10.1002/anie.201711126

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.
• Biaryl hydroxy aldehydes as intermediates in the metal-assisted atropo-enantioselective reduction of biaryl lactones: Structures and aldehyde-lactol equilibria
  作者：Gerhard Bringmann、Matthias Breuning、Heike Endress、Daniel Vitt、Karl Peters、Eva-Maria Peters

  DOI：10.1016/s0040-4020(98)00618-8

  日期：1998.9

  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.
• Ruthenium-Catalyzed Atropoenantioselective Synthesis of Axial Biaryls via Reductive Amination and Dynamic Kinetic Resolution
  作者：Donghui Guo、Jianwei Zhang、Bei Zhang、Jian Wang

  DOI：10.1021/acs.orglett.8b02785

  日期：2018.10.5

  via a cascade transfer hydrogenation and dynamic kinetic resolution strategy is described. This protocol features broad substrate scope and good functional group tolerance and allows the rapid assembly of axially chiral biaryls in good to high yields with high to excellent enantioselectivities. In addition, such structural motifs may have potential applications in enantioselective catalysis as chiral

  描述了通过级联转移氢化和动态动力学拆分策略，空前的钌催化的烷基胺对醛的对苯二酸选择性还原胺化反应。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高至高收率和高至优异的对映选择性快速组装轴向手性联芳基。另外，这样的结构基序可以作为手性配体或催化剂在对映选择性催化中具有潜在的应用。
• Atropoenantioselective Redox-Neutral Amination of Biaryl Compounds through Borrowing Hydrogen and Dynamic Kinetic Resolution
  作者：Jianwei Zhang、Jian Wang

  DOI：10.1002/anie.201711126

  日期：2018.1.8

  triggered by a cascade of borrowing hydrogen and dynamic kinetic resolution under the cooperative catalysis of a chiral iridium complex and an achiral Brønsted acid. This protocol features broad substrate scope and good functional‐group tolerance, and allows the rapid assembly of axially chiral biaryl compounds in good to high yields and with high to excellent enantioselectivity.

  我们在此报告了一种新颖的对芳基化合物的新型对苯二酚选择性氧化还原中性胺化反应，该反应是由手性铱配合物和非手性布朗斯台德酸的协同催化下的借入氢和动态动力学拆分级联触发的。该方案具有广泛的底物范围和良好的官能团耐受性，并允许以高至高收率和高至优异的对映选择性快速组装轴向手性联芳基化合物。