(M)-2-bromomethyl-1-(2'-benzyloxy-4',6'-dimethylphenyl)naphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (M)-2-bromomethyl-1-(2'-benzyloxy-4',6'-dimethylphenyl)naphthalene
• 英文别名: 2-(bromomethyl)-1-(2,4-dimethyl-6-phenylmethoxyphenyl)naphthalene
• 化学式: C₂₆H₂₃BrO
• 分子量: 431.372
• InChiKey: FLTJBWDCHJTWMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (M)-2-bromomethyl-1-(2'-benzyloxy-4',6'-dimethylphenyl)naphthalene 在 palladium on activated charcoal 三乙烯二胺 、 palladium diacetate 、 甲酸铵 、 N,N-二异丙基乙胺 、 1,4-双(二苯基膦)丁烷 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 24.0h， 生成 (M)-2-ethoxymethyl-1-(4',6'-dimethyl-2'-(diphenylphosphinyl)phenyl)naphthalene
  参考文献：
  名称：

  “内酯法”：对映体的新型P，N-联芳基配体的制备及其在合成二元生物碱，顺式鸟嘌呤B和顺式乙胺酸A中的用途

  摘要：

  “内酯法”是用于轴向手性联芳基的对映选择性合成的通用工具。强调了该概念的潜力和范围，特别是在其用于制备天然产物和手性助剂方面。作为一种新的应用，描述了对映体纯形式的新型轴向手性膦胺的合成。这些配体用于二元天然产物ancistrotanzanine B和ancistroealaine A的分子部分的不对称Suzuki交叉偶联。

  DOI：

  10.1016/j.tet.2003.12.070
• 作为产物：
  描述：

  2-(2-(hydroxymethyl)naphthalen-1-yl)-3,5-dimethylphenol 在 lithium aluminium tetrahydride 、 1,2-二溴四氯乙烷 、 caesium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 13.5h， 生成 (M)-2-bromomethyl-1-(2'-benzyloxy-4',6'-dimethylphenyl)naphthalene
  参考文献：
  名称：

  Enantioselective addition of diethylzinc to aldehydes using novel axially chiral 2-aminomethyl-1-(2′-hydroxyphenyl)naphthalene catalysts [1]

  摘要：

  The synthesis of atropo-enantiomerically pure aminomethyl and hydroxymethyl substituted biaryls derivatives M-2 and M-3 (and, optionally, their enantiomers), by dynamic kinetic resolution of a racemic lactone precursor, is described. Their application as chiral catalysts in the asymmetric addition of diethylzinc to aldehydes leads to excellent enantiomeric ratios of up to 99:1 and high chemical yields. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00020-2

文献信息

• Synthesis of Axially Chiral Biaryls by Atropo-Diastereoselective Cleavage of Configurationally Unstable Biaryl Lactones with Menthol-DerivedO-Nucleophiles
  作者：Gerhard Bringmann、Matthias Breuning、Rainer Walter、Andreas Wuzik、Karl Peters、Eva-Maria Peters

  DOI：10.1002/(sici)1099-0690(199911)1999:11<3047::aid-ejoc3047>3.0.co;2-o

  日期：1999.11

  Configurationally unstable lactone-bridged biaryls 4 are cleaved atropo-diastereoselectively using chiral menthol-derived alkali metal alkoxides, to give axially chiral biaryl esters of type 5 in high yields and excellent diastereomeric ratios of up to > 99:1. The method permits the optional preparation of each of the two atropisomers from the same lactone precursor (“atropo-divergence”), simply according

  使用手性薄荷醇衍生的碱金属醇盐选择性地将构型不稳定的内酯桥连的联芳基4裂解为对映体-非对映异构体，从而以高收率和高达> 99：1的极佳非对映异构体比例得到轴向类型5的轴向手性联芳基酯。该方法只需根据适当的薄荷酸酯或其对映异构体（如O-亲核试剂）的选择，或通过使用薄荷酸酯，就可以从同一内酯前体中任选地制备两种阻转异构体中的每一种（“阻转性”）。溶液或悬浮液。可能形成的不希望的次要阻转异构体5（如果有的话）可以通过环化回内酯4进行再循环（“轴向手性经济”）。。为了制备大量对映体纯的联芳醇9，开发了一种有效的反应序列：4的醇解原位还原结晶。这些醇解反应对于不对称联芳基合成的合成值通过将5转化为一系列具有对轴正交的各种官能团的6型对映纯联芳基进行说明。
• Synthesis and antitrypanosomal activity of 2-aminomethyl-1-(2-oxyphenyl)naphthalenes
  作者：Gerhard Bringmann、Robert-Michael Pfeifer、Petra Schreiber、Kristina Hartner、Nikolaus Kocher、Reto Brun、Karl Peters、Eva-Maria Peters、Matthias Breuning

  DOI：10.1016/j.tet.2004.05.076

  日期：2004.7

  A broad variety of enantiopure, axially chiral 2-aminomethyl-1-(2-oxyphenyl)naphthalenes were prepared via short and efficient synthetic pathways by using the 'lactone method' for the regio- and stereoselective construction of the biaryl axis. Their in vitro activity against Trypanosoma cruzi the causative agent of Chagas' disease, was evaluated. In particular, the M-configured atropisomers, with the 2-oxy function equipped with an O-triflate group, were found to exhibit good antitrypanosomal activities (down to IC50=1.6 mug/mL), combined with low levels of cytotoxicity. (C) 2004 Elsevier Ltd. All rights reserved.
• Atropo-enantioselective synthesis of a C3-symmetric tripodal ligand with three axially chiral biaryl subunits
  作者：Gerhard Bringmann、Matthias Breuning、Robert-Michael Pfeifer、Petra Schreiber

  DOI：10.1016/s0957-4166(03)00406-3

  日期：2003.8

  In contrast to the numerous successful applications of C-2-symmetric biaryls as powerful tools for asymmetric synthesis, there have so far been only few reports on combinations of C-3-symmetry with axial chirality. We present here the first enantioselective synthesis of a novel family of tripodal ligands containing three axially chiral biaryl subunits in an (M,M,M)- or, optionally, (P,P,P)-configured form. The incorporation of a PCl2- and a TiCl-fragment into the central cavity was achieved. (C) 2003 Elsevier Ltd. All rights reserved.
• Enantioselective addition of diethylzinc to aldehydes using novel axially chiral 2-aminomethyl-1-(2′-hydroxyphenyl)naphthalene catalysts [1]
  作者：Gerhard Bringmann、Matthias Breuning

  DOI：10.1016/s0957-4166(98)00020-2

  日期：1998.2

  The synthesis of atropo-enantiomerically pure aminomethyl and hydroxymethyl substituted biaryls derivatives M-2 and M-3 (and, optionally, their enantiomers), by dynamic kinetic resolution of a racemic lactone precursor, is described. Their application as chiral catalysts in the asymmetric addition of diethylzinc to aldehydes leads to excellent enantiomeric ratios of up to 99:1 and high chemical yields. (C) 1998 Elsevier Science Ltd. All rights reserved.
• The ‘lactone method’: enantioselective preparation of novel P,N-biaryl ligands and their use in the synthesis of the biarylic alkaloids, ancistrotanzanine B and ancistroealaine A
  作者：Gerhard Bringmann、Robert-Michael Pfeifer、Petra Schreiber、Kristina Hartner、Michaela Schraut、Matthias Breuning

  DOI：10.1016/j.tet.2003.12.070

  日期：2004.5

  The ‘lactone method’ is a versatile tool for the atroposelective synthesis of axially chiral biaryls. The potential and scope of the concept are highlighted, in particular with respect to its use in the preparation of natural products and chiral auxiliaries. As a new application, the synthesis of novel axially chiral phosphineamines in enantiopure form is described; these ligands were used in the asymmetric

  “内酯法”是用于轴向手性联芳基的对映选择性合成的通用工具。强调了该概念的潜力和范围，特别是在其用于制备天然产物和手性助剂方面。作为一种新的应用，描述了对映体纯形式的新型轴向手性膦胺的合成。这些配体用于二元天然产物ancistrotanzanine B和ancistroealaine A的分子部分的不对称Suzuki交叉偶联。