Pinan-2α,3β-diol | 21803-49-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Pinan-2α,3β-diol
• 英文别名: (1S,2S,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol
• CAS: 21803-49-6
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: MOILFCKRQFQVFS-GHCJXIJMSA-N

物化性质

• 沸点：
  263.7±8.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Pinan-2α,3β-diol 在 lead(IV) tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 以27%的产率得到[(1S,3S)-3-乙酰基-2,2-二甲基环丁基]乙酸
  参考文献：
  名称：

  次氯酸钠五水合物作为裂解反式环乙二醇的试剂

  摘要：

  次氯酸钠五水合物（NaOCl·5H 2 O）可用于有效地裂解跨环二醇，通常对这种转化具有抵抗力。有趣的是，顺式环二醇与NaOCl·5H 2 O的反应比相应的反式异构体的反应慢。这种反式选择性与用于裂解乙二醇的传统氧化剂形成鲜明对比。无环二醇还可以与NaOCl·5H 2 O有效反应，以高收率形成其相应的羰基化合物。

  DOI：

  10.1021/acs.joc.9b01132
• 作为产物：
  描述：

  (+)-α-蒎烯 在 sodium tetrahydroborate 、 potassium permanganate 作用下， 生成 Pinan-2α,3β-diol
  参考文献：
  名称：

  Synthesis and stereochemistry of the four isomeric pinane-2,3-diols

  摘要：

  DOI：

  10.1021/jo00815a028

文献信息

• A novel and efficient catalytic epoxidation of olefins and monoterpenes with microencapsulated Lewis base adducts of methyltrioxorhenium
  作者：Raffaele Saladino、Alessia Andreoni、Veronica Neri、Claudia Crestini

  DOI：10.1016/j.tet.2004.11.065

  日期：2005.1

  The reactivity of methyltrioxorhenium in the epoxidation of olefins can be tuned by the presence of Lewis bases as ligands of the metal center. Unfortunately, a large excess of ligand is usually required to obtain high yields and selectivities mainly because of the fluxional behaviour that these compounds show in solution. We describe here the microencapsulation technique that can resolve this problem

  甲基三氧or在烯烃的环氧化反应中的反应性可以通过路易斯碱作为金属中心的配体的存在来调节。不幸的是，通常需要大量过量的配体以获得高产率和选择性，这主要是因为这些化合物在溶液中表现出的通量行为。我们在这里描述可以解决此问题的微囊化技术。甲基三氧合ium与含氮配体的微囊化路易斯碱加合物是高效的选择性催化剂，即使在最敏感的底物情况下，也能用过氧化氢环氧化几种烯烃和单萜。这些系统显示了配体加速催化的优势以及非均相化合物的优势。
• Reactions of terpene alcohols and diols with chlorine dioxide in dimethylformamide
  作者：L. L. Frolova、A. V. Popov、L. V. Bezuglaya、I. N. Alekseev、P. A. Slepukhin、A. V. Kutchin

  DOI：10.1134/s107036321603018x

  日期：2016.3

  The system chlorine dioxide–dimethylformamide in combination with or without a catalytic amount of MoCl5, CeCl3, ZrOCl2, or VO(acac)2 induces oxidative chlorination of a number of bicyclic terpene alcohols and vicinal diols. 2α-Chloropinan-3-one, 3α-chloro-10β-pinan-4-one, 5α-chloro-3α-hydroxycaran-4-one, 5β-chloro-3β-hydroxycaran-4-one, and 4α-chloro-2α-hydroxypinan-3-one were thus synthesized in

  二氧化氯-二甲基甲酰胺体系与有或没有催化量的MoCl 5，CeCl 3，ZrOCl 2或VO（acac）2组合使用，会引起许多双环萜烯醇和邻二醇的氧化氯化反应。2α-氯丁酮3-one，3α-氯10β-pinan-4-one，5α-氯3α-hydroxycaran-4-one，5β-氯-3β-hydroxycaran-4-one和4α-chloro-2α因此以良好的制备产率合成了-羟基pinan-3-one。
• The Influence of Boryl Substituents on the Formation and Reactivity of Adjacent and Vicinal Free Radical Centers
  作者：John C. Walton、Andrew J. McCarroll、Qiao Chen、Bertrand Carboni、Roger Nziengui

  DOI：10.1021/ja9944812

  日期：2000.6.1

  (boronic esters), by addition to vinyl boronate, and by hydrogen abstraction from alkyldioxaborolanes and observed by EPR spectroscopy. Unsymmetrically substituted α-boronate radicals displayed selective line broadening in their low-temperature spectra from which barriers to internal rotation about •CH2−B(OR‘)OR bonds were found to be 3 ± 1 kcal mol-1. Use of an empirical relationship between barrier height

  通过从 1-溴烷基二氧杂硼烷（硼酸酯）中提取溴、添加到硼酸乙烯酯以及从烷基二氧杂硼烷中提取氢并通过 EPR 光谱观察，可以生成含有 α-硼酸酯取代基的自由基。不对称取代的 α-硼酸酯自由基在其低温光谱中显示出选择性谱线加宽，从中发现关于 •CH2-B(OR')OR 键的内旋障碍为 3 ± 1 kcal mol-1。使用势垒高度和键离解能之间的经验关系导致 BDE[(RO)2BCH2-H] = 98.6 kcal mol-1。叔丁氧基自由基从 2,4,4,5,5-pentamethyl-1,3,2-dioxaborolane 夺氢的速率常数是根据竞争性 EPR 和产品研究确定的，发现相对较小，与未活化的速率常数相当甲基。发现从双（4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基）甲烷中提取氢极其困难。α-硼酸盐自由基的结构和能量...
• Oxidation of terpenoid diols with chlorine dioxide: Preparation of ketols and α-chlorohydroxyketones of carane and pinane structures
  作者：L. L. Frolova、A. V. Popov、L. V. Bezuglaya、I. N. Alekseev、P. A. Slepukhin、A. V. Kuchin

  DOI：10.1134/s1070363213080124

  日期：2013.8

  Vicinal terpenoid diols of carane- and pinane-type structures have been oxidized with chlorine dioxide in pyridine to form the corresponding ketols in the preparative yield of 52-72%, the selectivity of alpha-hydroxyketones formation being 80-90%. It has been shown that the diols reactivity towards oxidation with ClO2 depends mainly on the stereochemistry of hydroxy groups. The catalysts, VO(acac)(2), Mo(CO6), and MoCl5 have practically no effect on the oxidation process. When the reaction has been performed in dimethylformamide, the hydroxyketone chlorination occurred at high conversion.
• Broad Spectrum β-Lactamase Inhibition by a Thioether Substituted Bicyclic Boronate
  作者：Anete Parkova、Anka Lucic、Alen Krajnc、Jürgen Brem、Karina Calvopiña、Gareth W. Langley、Michael A. McDonough、Peteris Trapencieris、Christopher J. Schofield

  DOI：10.1021/acsinfecdis.9b00330

  日期：2020.6.12

  beta-Lactamases comprise the most widely used mode of resistance to beta-lactam antibiotics. Cyclic boronates have shown promise as a new class of beta-lactamase inhibitor, with pioneering potential to potently inhibit both metallo- and serine-beta-lactamases. We report studies concerning a bicyclic boronate ester with a thioether rather than the more typical beta-lactam antibiotic "C-6/C-7" acylamino type side chain, which is present in the penicillin/cephalosporin antibiotics. The thioether bicyclic boronate ester was tested for activity against representative serine- and metallo-beta-lactamases. The results support the broad inhibition potential of bicyclic boronate based inhibitors with different side chains, including against metallo-beta-lactamases from B1, B2, and B3 subclasses. Combined with previous crystallographic studies, analysis of a crystal structure of the thioether inhibitor with the clinically relevant VIM-2 metallo-beta-lactamase implies that further SAR work will expand the already broad scope of beta-lactamase inhibition by bicyclic boronates.