(2S*,3S*)-1-(Tosyloxy)-2,3-epoxyhexane

• 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: (2S*,3S*)-1-(Tosyloxy)-2,3-epoxyhexane
• 英文别名: (+/-)-(2S*,3S*)-3-Propyloxiran-2-ylmethyl 4-methylbenzenesulfonate；(+/-)-2--(2S*,3S*)-3-propyloxirane；trans-3-propyl-2-tosyloxymethyloxirane；[(2S,3S)-3-propyloxiran-2-yl]methyl 4-methylbenzenesulfonate
• 化学式: C₁₃H₁₈O₄S
• 分子量: 270.35
• InChiKey: QDPITHJQVMFWHD-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S*,3S*)-1-(Tosyloxy)-2,3-epoxyhexane 在 copper(l) iodide 、 偶氮二异丁腈 、 三正丁基氢锡 、 magnesium iodide 作用下， 反应 3.5h， 生成 1-苯基-2-己醇
  参考文献：
  名称：

  C-1 Reactivity of 2,3-Epoxy Alcohols via Oxirane Opening with Metal Halides: Applications and Synthesis of Naturally Occurring 2,3-Octanediol, Muricatacin, 3-Octanol, and 4-Dodecanolide

  摘要：

  The C-1 reactivity of 2,3-epoxy alcohols and derivatives has been examined thoroughly. In the first approach a rearrangement opening of 2,3-epoxy alcohols with LiI leads to 1-iodo 2,3-diols with erythro or three stereochemistry starting from trans or cis epoxy alcohols. Subsequent coupling with a carbon nucleophile can lead to a series of vicinal diols with predicted relative and absolute stereochemistry: the described methodology has been applied to the asymmetric synthesis of the naturally occurring (S,S)-2,3-octanediol and (R,R)-muricatacin. The second approach, starting from easily available tosyloxy epoxides, leads to the highly regioselective opening of the oxirane ring with Li halides. The 3-iodohydrins obtained can be reduced to the corresponding 1-(tosyloxy)alkan-2-ols and then coupled with common carbon nucleophiles to afford, in high yields, optically active alcohols. This methodology has been applied to the asymmetric synthesis of naturally occurring pheromones like 3(R)-octanol and 4(R)-dodecanolide.

  DOI：

  10.1021/jo00120a025
• 作为产物：
  描述：

  对甲苯磺酰氯 、 反式-2-已烯-1-醇 生成 (2S*,3S*)-1-(Tosyloxy)-2,3-epoxyhexane
  参考文献：
  名称：

  Balmer, Ethnie; Germain, Andrew; Jackson, William P., Journal of the Chemical Society. Perkin transactions I, 1993, # 4, p. 399 - 400

  摘要：

  DOI：

文献信息

• Lewis acid induced rearrangement of 2,3-epoxy sulfides; regiospecific trapping of thiiranium ion intermediates with nitrogen heterocycles and amides. Use of imines as nucleophilic equivalents for the selective monoalkylation of primary amines
  作者：Duncan M Gill、Neil A Pegg、Christopher M Rayner

  DOI：10.1016/0040-4020(96)00036-1

  日期：1996.3

  The Lewis acid induced conversion of 2,3-epoxy sulfides into the corresponding 3-trimethylsilyloxy-1,2-thiiranium ions is described. Such intermediates react with silylated nitrogen heterocycles and amides regiospecifically to form 1-substituted-3-hydroxy-2-thioethers in good to moderate yields with full stereochemical control. Exclusive N-alkylation is observed. When simple primary amines are used

  描述了路易斯酸诱导的2，3-环氧硫化物到相应的3-三甲基甲硅烷氧基-1，2-噻吩鎓离子的转化。这样的中间体与甲硅烷基化的氮杂环和区域特异性的酰胺反应，以完全中等的化学控制，以良好至中等的产率形成1-取代的3-羟基-2-硫醚。观察到排他的N-烷基化。当简单的伯胺用作亲核试剂时，仅分离出多烷基化产物。但是，亚胺可以有效地用作伯胺的亲核当量，最初形成的亚胺离子很容易被碱水溶液水解而释放出仲胺，这是伯胺整体选择性单烷基化的产物。
• ZnCl₂as an Efficient Catalyst in the Thiolysis of 1,2-Epoxides by Thiophenol in Aqueous Medium
  作者：Ferdinando Pizzo、Luigi Vaccaro、David Amantini、Francesco Fringuelli、Simone Tortoioli

  DOI：10.1055/s-2003-42107

  日期：——

  ZnCl2 (5 mol%) is an efficient catalyst for the thiolysis of 1,2-epoxides by thiophenol in water at pH 4.0. A variety of β-hydroxy phenylsulfides were obtained in short reaction times and excellent yields. Starting from cyclohexene oxide (1), two one-pot multi-step procedures in sole water (thiolysis/oxidation with H2O2) have been realized, for the chemoselective synthesis of the corresponding β-hydroxysulfoxides 19 or for the related β-hydroxysulfone 20.

  ZnCl2（5 mol%）是一种有效的催化剂，用于在pH 4.0的水相中通过硫苯醇对1,2-环氧化物进行硫解反应。在短反应时间内获得了多种β-羟基苯硫醚，并且产率非常高。从环己烯氧化物（1）出发，已经实现了在纯水中进行的两步一锅法（硫解/用H2O2氧化），用于选择性合成相应的β-羟基亚砜19或相关的β-羟基磺酰20。
• Highly Regioselective Ring Opening of 2,3-Epoxy Alcohol Methanesulfonates
  作者：Lian-xun Gao、Hitoshi Saitoh、Fei Feng、Akio Murai

  DOI：10.1246/cl.1991.1787

  日期：1991.10

  Reaction of 2,3-epoxy-1-ol methanesulfonates with diethylaluminum chloride or with the mixture of diethylaluminum chloride and diethylamine hydrobromide in dichloromethane gave rise to regioselectively the corresponding 3-chloro- and 3-bromo-1,2-diol 1-methanesulfonates, respectively, in excellent yields.

  将 2,3-环氧-1-醇甲烷磺酸盐与二乙基氯化铝或二乙基氯化铝与氢溴酸二乙胺的混合物在二氯甲烷中反应，可分别得到相应的 3-氯和 3-溴-1,2-二醇 1-甲烷磺酸盐，且产量极高。
• Hexafluoroisopropanol-Mediated Intramolecular Ring-Opening Cyclization of Indolyl-<i>N</i>-Tethered Epoxides: Tether-Length-Controlled Synthesis of 1,7- and 1,2-Fused Indoles
  作者：Arup Jyoti Das、Raju Chouhan、Sajal Kumar Das

  DOI：10.1021/acs.joc.1c00721

  日期：2021.6.18

  position of the indole and epoxide substituents and the tether length separating these two reacting moieties have strong effects on the cyclization. This mild and transition-metal-free protocol delivered pyrrolo[3,2,1-ij]quinolin-5-ols in moderate to good yields from substrates bearing both a methylene linker that connects the indole and epoxide moieties and an electron-rich indole carbocyclic ring. Notably

  尽管能够以完全原子经济性和高化学选择性、区域选择性、对映选择性和非对映选择性构建苯并稠合杂环，但分子内弗里德尔-克拉夫茨环氧化物芳烃环化（IFCEAC）在有机合成中仍未得到充分利用。因此，这种强大的 Csp 2 -Csp 3键形成反应的广泛适应性需要对底物范围有广泛的了解，以更好地影响杂环合成。沿着这条路线，我们研究了 IFCEAC 在合成 1,7- 和 1,2-稠合吲哚中的适用性。在本文中，我们报告了我们对六氟-2-丙醇 (HFIP) 介导的易于获得的吲哚基-N 的IFCEAC 的第一个例子的范围和局限性的系统调查结果- 束缚环氧化物。我们观察到吲哚和环氧化物取代基的性质和位置以及分隔这两个反应部分的系链长度对环化有很强的影响。这种温和且不含过渡金属的方案从带有连接吲哚和环氧化物部分的亚甲基接头和富电子吲哚的底物中以中等至良好的产率提供吡咯并[3,2,1- ij ]喹啉-5-醇碳环。值得
• Switching of regioselectivity in base-mediated diastereoselective annulation of 2,3-epoxy tosylates and their <i>N</i>-tosylaziridine analogs with 2-mercaptobenzimidazole
  作者：Arup Jyoti Das、Hemi Borgohain、Bipul Sarma、Sajal Kumar Das

  DOI：10.1039/c9ob02454a

  日期：——

  intermolecular alkylation followed by an N-C3 bond-forming, endo-selective intramolecular epoxide ring-opening cyclization reaction. A spectacular regioselectivity switching (tandem S-C3 and N-C1 bond formation reactions) was observed with related trans-N-tosylaziridine substrates. Wide substrate scope, complete diastereoselectivity, high to complete regioselectivity and mild transition metal-free conditions

  已开发出一种由碱介导的易于接近的2，3-环氧甲苯磺酸盐与2-巯基苯并咪唑的二亲核环化反应，用于一锅非对映选择性合成基于苯并咪唑的三环化合物，该化合物具有两个立体异构中心。对于在C3位置带有芳基或烷基取代基的反式底物，该反应涉及初始的形成S-C1键的分子间烷基化，然后进行形成N-C3键的内选择性分子内环氧化物开环环化反应。在相关的反式-N-甲苯磺酰氮丙啶底物上观察到了惊人的区域选择性转换（串联S-C3和N-C1键形成反应）。宽的底物范围，完全的非对映选择性，高至完全的区域选择性以及温和的无过渡金属条件，使得该方案特别有效和实用。