2,2,6-trimethylchroman-3-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2,2,6-trimethylchroman-3-ol
• 英文别名: 2,2,6-Trimethyl-3,4-dihydrochromen-3-ol
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: UCEVSCKMRSONMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基-3-丁烯-2-醇 在 bis(acetylacetonate)oxovanadium 吡啶 、 2,4,6-三甲基吡啶 、 叔丁基过氧化氢 、 lithium aluminium tetrahydride 、 磺酰氯 、 Raney Ni(W₄) 、 sodium hydride 、 对甲苯磺酸 、 三乙胺 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 苯 为溶剂， 反应 58.75h， 生成 2,2,6-trimethylchroman-3-ol
  参考文献：
  名称：

  Diastereoselective Synthesis of (2S*,3R*)- and (2R*,3R*)-2,6-Dimethyl-2-homoprenylchroman-3-ol

  摘要：

  通过对 ortho-(2,3-环氧烷基)苯酚的立体选择性开环环化合成了 (2S*,3R*)- 和 (2R*,3R*)-2,2-双烷基色烯醇，这些苯酚是通过对对甲酚与 (2R*,3R*)- 和 (2R*,3S*)-2,3-双乙酰氧烷基异丙基硫化物的偶联制备而成，而这些硫化物又分别源自香叶醇和紫罗兰醇。

  DOI：

  10.1055/s-1998-1751

文献信息

• Activating tert-butyl hydroperoxide by chelated vanadates for stereoselectively preparing sidechain-functionalized tetrahydrofurans
  作者：Maike Dönges、Matthias Amberg、Mark Niebergall、Jens Hartung

  DOI：10.1016/j.jinorgbio.2015.04.009

  日期：2015.6

  tert-Butyl hydroperoxide (TBHP) stereoselectively oxidizes substituted 4-pentenols, when activated by (ethyl)[cis-(piperidine-2,6-diyl)dimethyl] vanadates. The reaction affords (tetrahydrofuran-2-yl)methanols in up to 89% yield, and in stereoselectivity ranging between moderate (cis:trans = 32:68) to excellent (>99:1). Correlating structures of 4-pentenols, differing by substitution at tetragonal and trigonal stereocenters, to configuration of products obtained from oxidative cyclization provides a reaction model explaining the origin of stereoselectivity by (i) intramolecular oxygen atom transfer to (ii) a chair-like folded alkenol, being (iii) hydrogen-bonded to one of the two aminodiolate oxygens of the chelated vanadate, having (iv) substituents in the chair-like transition structure preferentially aligned equatorially. Substituents at trigonal stereocenters improve 2,5-cis- and 2,4-trans-selectivity for oxidative 4-pentenol cyclization in case of (Z)-configuration. An (E)-substituent does not alter selectivity exerted by a terminal (Z)-substituent of similar steric size. Larger (E)-groups increase the fraction of 2,5-trans-cyclized products. The reaction model additionally implements results from vanadium-51 NMR spectroscopy and density functional theory. According to theory, the (dialkoxy)(oxo)vanadium substituent exerts in the preferred end-on conformation almost no effect on structure and bonding of the peroxide group in tert-butylperoxy vanadates. Changing conformation to a higher in energy side-on arrangement puts the vanadate-bound tert-butylperoxy group into a position to serve in a concerted reaction as combined electron acceptor and oxygen atom donor. (C) 2015 Elsevier Inc. All rights reserved.
• Diastereoselective Synthesis of (2<i>S</i>*,3<i>R</i>*)- and (2<i>R</i>*,3<i>R</i>*)-2,6-Dimethyl-2-homoprenylchroman-3-ol
  作者：Seiichi Inoue、Masatoshi Asami、Kiyoshi Honda、Kedar Shanker Shrestha、Masaaki Takahashi、Takashi Yoshino

  DOI：10.1055/s-1998-1751

  日期：1998.6

  Diastereoselective synthesis of (2S*,3R*)- and (2R*,3R*)-2,2-dialkylchroman-3-ols was achieved by stereoselective epoxide-opening cyclization of ortho-(2,3-epoxyalkyl)phenols which were prepared by the coupling of p-cresol and (2R*,3R*)- and (2R*,3S*)-2,3-diacetoxyalkyl isopropyl sulfides, which were in turn derived from geraniol and nerol, respectively.

  通过对 ortho-(2,3-环氧烷基)苯酚的立体选择性开环环化合成了 (2S*,3R*)- 和 (2R*,3R*)-2,2-双烷基色烯醇，这些苯酚是通过对对甲酚与 (2R*,3R*)- 和 (2R*,3S*)-2,3-双乙酰氧烷基异丙基硫化物的偶联制备而成，而这些硫化物又分别源自香叶醇和紫罗兰醇。