5-hydroxymethyl-1-p-toluenesulfonyl-1,2,3,6-tetrahydropyridine | 1234835-92-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-hydroxymethyl-1-p-toluenesulfonyl-1,2,3,6-tetrahydropyridine
• 英文别名: 3-hydroxymethyl-N-tosyl-1,2,5,6-tetrahydropyridine；3-hydroxymethyl-1-(4-methylphenylsulfonyl)-1,2,5,6-tetrahydropyridine；[1-(4-methylphenyl)sulfonyl-3,6-dihydro-2H-pyridin-5-yl]methanol
• CAS: 1234835-92-7
• 化学式: C₁₃H₁₇NO₃S
• 分子量: 267.349
• InChiKey: IJBPPJKDHVVZRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-hydroxymethyl-1-p-toluenesulfonyl-1,2,3,6-tetrahydropyridine 在 sodium cyanoborohydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 3-hydroxymethyl-1-(4-methylphenylsulfonyl)piperidin-3-ol
  参考文献：
  名称：

  Approaches to 3,4,5-substituted piperidines via 1,2,5,6-tetrahydropyridines prepared by ring-closing metathesis

  摘要：

  Synthetic approaches to (1RS,2SR,6SR)-7-arylmethyl-2-alkoxymethyl-4,7-diaza-9-oxabicyclo[4.3.0] nonan-8-ones, potentially selective muscarinic M-1 receptor agonists, by hydration of 1,2,5,6-tetrahydropyridines were investigated. 3-Substituted N-tosy1-1,2,5,6-tetrahydropyridines were prepared by ring-closing metathesis (RCM). The direct hydration of these by hydroboration-oxidation was not usefully selective, but cis-3-hydroxymethyl-4-tert-butyldimethylsilyloxy-N-tosylpiperidine was prepared from 3-hydroxymethyl-N-tosy1-1,2,5,6-tetrahydropyridine by epoxidation, mesylation, reductive elimination, silylation and hydroboration-oxidation. Problems were encountered during attempts to prepare 3-alkoxymethyl-1,2,5,6-tetrahydropyridines with protected amino and cyclobutyl substituents at C5 by ring-closing metathesis, perhaps because of steric hindrance. Nevertheless interesting chemistry was encountered during the synthesis of the RCM precursors including a novel coupling via a 2-ethenyl-N-nosylaziridine and the formation of an oxaazathiocin by an intramolecular substitution of the nitro group of an N-nosyl protected amine by a proximate hydroxyl substituent. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.11.040
• 作为产物：
  描述：

  氢溴酸槟榔碱 在 二异丁基氢化铝 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 43.33h， 生成 5-hydroxymethyl-1-p-toluenesulfonyl-1,2,3,6-tetrahydropyridine
  参考文献：
  名称：

  四环Diquinane集体全合成石松Paniculatine，（ - - ） - Magellanine，（+） - Magellaninone及其类似物生物碱（+）

  摘要：

  四环diquinane的集体总合成石松生物碱，（+） - paniculatine，（ - ） - magellanine，（+） - magellaninone，以及两个类似物（ - ） - 13-外延-paniculatine和（+） - 3-羟基-13 -dehydro-paniculatine，已经完成。通过在C-3 paniculatine的战略上有用的羟基的逻辑引导另外，强大的四环核心迅速合成利用位点特异性和立体选择性醛醇环化，从而使ABD→ABCD四环方法diquinane石松生物碱可达到的第一次。

  DOI：

  10.1021/ol502679v

文献信息

• Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
  作者：J. Johan Verendel、Jia-Qi Li、Xu Quan、Byron Peters、Taigang Zhou、Odd R. Gautun、Thavendran Govender、Pher G. Andersson

  DOI：10.1002/chem.201104073

  日期：2012.5.21

  Several types of chiral hetero‐ and carbocyclic compounds have been synthesized by using the asymmetric hydrogenation of cyclic alkenes. N,P‐Ligated iridium catalysts reduced six‐membered cyclic alkenes with various substituents and heterofunctionality in good to excellent enantioselectivity, whereas the reduction of five‐membered cyclic alkenes was generally less selective, giving modest enantiomeric

  通过使用环状烯烃的不对称氢化，已经合成了几种类型的手性杂环和碳环化合物。N，P连接的铱催化剂将具有各种取代基和杂官能团的六元环烯烃还原为良好至优异的对映选择性，而五元环烯烃的还原通常选择性较低，给出适度的对映异构体过量。氢化的立体选择性在很大程度上取决于五元环烯烃而不是六元环烯烃的底物结构。六元烯烃还原反应中形成的主要对映异构体可通过选择性模型预测，异构体烯烃具有互补的对映选择性，氢化后可得到相反的旋光异构体。顺式环己烷羧酸盐。
• Rhodium(I)-Catalyzed Decarbonylative Spirocyclization through CC Bond Cleavage of Benzocyclobutenones: An Efficient Approach to Functionalized Spirocycles
  作者：Tao Xu、Nikolas A. Savage、Guangbin Dong

  DOI：10.1002/anie.201310149

  日期：2014.2.10

  The rhodium‐catalyzed formation of all‐carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal–ligand combination [Rh(CO)2Cl}2]/P(C6F5)3 catalyzed this transformation most efficiently. A range of diverse spirocycles were synthesized in good to excellent yields and many sensitive functional groups were tolerated

  铑催化的全碳螺中心的形成涉及三取代环烯烃和苯并环丁烯酮通过C → C活化的脱羰偶联。金属-配体组合[Rh(CO) 2 Cl} 2 ]/P(C 6 F 5 ) 3最有效地催化该转化。合成了一系列不同的螺环，收率良好至优异，并且可以耐受许多敏感官能团。机理研究支持通过 β-H 消除/脱羰途径发生的氢转移过程。
• Highly Flexible Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation
  作者：J. Johan Verendel、Taigang Zhou、Jia-Qi Li、Alexander Paptchikhine、Oleg Lebedev、Pher G. Andersson

  DOI：10.1021/ja103901e

  日期：2010.7.7

  A range of saturated chiral azacycles has been prepared in high yield and with high selectivity from simple starting materials. A modular approach with ring-closing metathesis as a key step was used to produce a number of five-, six-, and seven-membered cyclic alkenes. Asymmetric hydrogenation catalyzed by N,P-ligated iridium complexes gave saturated azacycles in high optical purity. This methodology

  一系列饱和手性氮杂环已从简单的原料中以高产率和高选择性制备。以闭环复分解为关键步骤的模块化方法被用于生产许多五元、六元和七元环烯烃。N,P-连接的铱配合物催化的不对称氢化得到高光学纯度的饱和氮杂环。这种方法在药物前体的合成中得到了证明。
• Gold-Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross-Coupling Reactivity with Gold
  作者：Mark D. Levin、F. Dean Toste

  DOI：10.1002/anie.201402924

  日期：2014.6.10

  the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetalation, CBr oxidative addition, and CC reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development

  描述了在没有牺牲氧化剂的情况下由金催化的sp 3 –sp 2 C  C 交叉偶联反应。该方法成功的关键是采用带有双（膦基）胺配体的双金属催化剂。提出了一个机制假设，并显示了模型金配合物中可观察到的金属转移、C  Br 氧化加成和 C  C 还原消除。我们预计这种方法将成为开发涉及氧化还原活性金催化剂的新型转化的平台。
• CHEMICAL INHIBITORS OF CHOLESTEROL BIOSYNTHESIS AND VENOUS ANGIOGENESIS
  申请人：Kwon Ohyun

  公开号：US20130289073A1

  公开（公告）日：2013-10-31

  This invention relates, e.g., to a compound, aplexone, and pharmaceutically acceptable salts and solvates, and functional variants, thereof. Methods of using the compounds and pharmaceutical compositions comprising them, e.g. to inhibit angiogenesis and to reduce cellular cholesterol levels, are also included.