1-(4-methoxyphenyl)-5-methylhexan-3-ol | 26496-86-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(4-methoxyphenyl)-5-methylhexan-3-ol
• CAS: 26496-86-6
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: UFIYLHSJBUISPY-UHFFFAOYSA-N

物化性质

• 沸点：
  173 °C(Press: 12 Torr)
• 密度：
  0.979±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(4-methoxyphenyl)-5-methylhexan-3-ol 在 四溴化碳 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以85%的产率得到1-(3-Bromo-5-methyl-hexyl)-4-methoxy-benzene
  参考文献：
  名称：

  Cyclopentane Construction by Rh-Catalyzed Intramolecular C−H Insertion:  Relative Reactivity of a Range of Catalysts

  摘要：

  The preparation and Rh-mediated cyclization of the alpha-diazoester 1 are outlined, and its utility in determining the elements that contribute to the reactivity of the intermediate Rh-carbenoid is presented. The rate of disappearance of diazo ester 1 catalyzed by several representative Rh(II) complexes was determined. The observed relative rate constants for the reaction of the Rh(II) complexes with 1 varied over a range of >10(7). The reactivity of the Rh-carbenoid intermediate was explored using the ratio of the sum of (3 + 4 + 5) to 2 (cyclization vs elimination), the ratio of 3 to the sum of (4 + 5) (chemo selectivity), and the ratio of 4 to 5 (diastereoselectivity). It is striking that these four measures of reactivity were found to be independent of each other.

  DOI：

  10.1021/jo0303766
• 作为产物：
  描述：

  4-甲基-2-戊酮 在 palladium on activated charcoal sodium tetrahydroborate 、 氢气 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 6.16h， 生成 1-(4-methoxyphenyl)-5-methylhexan-3-ol
  参考文献：
  名称：

  Cyclopentane Construction by Rh-Catalyzed Intramolecular C−H Insertion:  Relative Reactivity of a Range of Catalysts

  摘要：

  The preparation and Rh-mediated cyclization of the alpha-diazoester 1 are outlined, and its utility in determining the elements that contribute to the reactivity of the intermediate Rh-carbenoid is presented. The rate of disappearance of diazo ester 1 catalyzed by several representative Rh(II) complexes was determined. The observed relative rate constants for the reaction of the Rh(II) complexes with 1 varied over a range of >10(7). The reactivity of the Rh-carbenoid intermediate was explored using the ratio of the sum of (3 + 4 + 5) to 2 (cyclization vs elimination), the ratio of 3 to the sum of (4 + 5) (chemo selectivity), and the ratio of 4 to 5 (diastereoselectivity). It is striking that these four measures of reactivity were found to be independent of each other.

  DOI：

  10.1021/jo0303766

文献信息

• Tris(acetylacetonato)rhodium(III)-Catalyzed α-Alkylation of Ketones, β-Alkylation of Secondary Alcohols and Alkylation of Amines with Primary Alcohols
  作者：Ponnam Satyanarayana、Ganapam Manohar Reddy、Hariharasharma Maheswaran、Mannepalli Lakshmi Kantam

  DOI：10.1002/adsc.201300061

  日期：2013.6.17

  The tris(acetylacetonato)rhodium(III) catalyst is shown to be a versatile catalyst in the presence of DABCO (1,4‐diazabicyclo[2.2.2]octane) as ligand for the α‐alkylation of ketones followed by transfer hydrogenation, for the one‐pot β‐alkylation of secondary alcohols with primary alcohols and for the alkylation of aromatic amines in the presence of an inorganic base in toluene.

  在DABCO（1,4-二氮杂双环[2.2.2]辛烷）作为配体的α-烷基化酮，然后进行转移氢化的情况下，三（乙酰丙酮基）铑（III）催化剂是一种多功能催化剂。仲醇与伯醇的单锅β-烷基化反应，以及在甲苯中存在无机碱的情况下芳族胺的烷基化反应。
• Heterocyclization involving benzylic C(sp³)–H functionalization enabled by visible light photoredox catalysis
  作者：Ganesh Pandey、Ramkrishna Laha、Pradip Kumar Mondal

  DOI：10.1039/c9cc04287c

  日期：——

  A general and efficient method for heterocyclization involving benzylic C(sp3)–H functionalization enabled by visible light photoredox catalysis to access a wide range of structurally diverse oxygen as well as nitrogen heterocycles up to a gram scale is reported. The potential application of this new methodology is demonstrated by the total synthesis of (−)-codonopsinine and (+)-centrolobine. Herein

  据报道，一种通用有效的杂环化方法涉及苄基C（sp 3）–H官能团，该官能团通过可见光光氧化还原催化作用可访问范围广泛的结构多样的氧和氮杂环，直至克级。（-）-codonopsinine和（+）-centrolobine的总合成证明了这种新方法的潜在应用。在本文中提出了与氟化试剂不同，selectfluor用作氧化猝灭剂和氢自由基受体。
• A General Catalyst for Site-Selective C(sp³)–H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp³)–H Bonds
  作者：Ryan J. Scamp、James G. Jirak、Nicholas S. Dolan、Ilia A. Guzei、Jennifer M. Schomaker

  DOI：10.1021/acs.orglett.6b01392

  日期：2016.6.17

  catalyst-controlled and selective carbon–hydrogen (C–H) bond amination of activated secondary C–H bonds over tertiary alkyl C(sp3)–H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into

  作为底物控制，发现能够促进活化的二级 C-H 键在叔烷基 C(sp 3 )-H 键上的一般、催化剂控制和选择性碳-氢 (C-H) 键胺化的过渡金属配合物的发现具有挑战性当涉及反应性氮烯中间体时，通常占主导地位。在这封信中，我们报告了一种新的银配合物 [(Py 5 Me 2 )AgOTf] 2的设计，该配合物在将氮烯插入炔丙基、苄基和烯丙基 C-H 键时表现出普遍和良好的选择性。叔烷基 C(sp 3 )-H 键。
• Inverting Steric Effects: Using “Attractive” Noncovalent Interactions To Direct Silver-Catalyzed Nitrene Transfer
  作者：Minxue Huang、Tzuhsiung Yang、Jonathan D. Paretsky、John F. Berry、Jennifer M. Schomaker

  DOI：10.1021/jacs.7b07619

  日期：2017.12.6

  directing the NT; computational studies support the involvement of π···π and Ag···π interactions between catalyst and substrate, primarily by lowering the energy of the directed transition state and reaction conformers. A simple Hess’s law relationship can be employed to predict selectivities for new substrates containing competing NCIs. The insights presented herein are poised to inspire the design of other

  硝基转移（NT）反应代表了将C–H键转换为许多商品化学品和药品中普遍存在的胺基的强大直接方法。C–N键的重要性刺激了许多过渡金属配合物的发展，以实现化学，区域和非对映选择性NT。一项持续的挑战是要了解催化剂与底物之间的微妙相互作用如何影响CH氨基化事件的位点选择性。在这项工作中，我们探究了Ag（tpa）OTf（tpa =三（吡啶基甲基）胺）倾向于在3°烷基C（sp 3上）激活α-共轭C–H键的根本原因。）-H键并将这些见解应用于反应优化和催化剂设计。实验结果表明非共价相互作用（NCI）可能在指导NT中的作用。计算研究主要通过降低有向过渡态和反应构象异构体的能量来支持催化剂与底物之间的π··π和Ag··ππ相互作用。简单的赫斯定律关系可以用来预测含有竞争性NCI的新底物的选择性。本文提出的见解有望激发其他催化剂控制的CHH功能化反应的设计。
• Ligand-Controlled, Tunable Silver-Catalyzed C–H Amination
  作者：Juliet M. Alderson、Alicia M. Phelps、Ryan J. Scamp、Nicholas S. Dolan、Jennifer M. Schomaker

  DOI：10.1021/ja5094309

  日期：2014.12.3

  The development of readily tunable and regioselective C-H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C-H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C-H amination.