(+/-)-(2R,6R)-2-benzyl-6-methyltetrahydro-2H-pyran | 138695-55-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+/-)-(2R,6R)-2-benzyl-6-methyltetrahydro-2H-pyran
• 英文别名: (2R*,6R*)-2-benzyl-6-methyl-tetrahydropyran；(+/-)-cis-2-benzyl-6-methyltetrahydropyran；cis-2-benzyl-6-methyltetrahydro-2H-pyran；cis-2-benzyl-6-methyltetrahydropyran；(2S,6S)-2-benzyl-6-methyloxane
• CAS: 138695-55-3
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: DGFMCGSJCXNAOB-AAEUAGOBSA-N

物化性质

• 沸点：
  277.1±9.0 °C(Predicted)
• 密度：
  0.971±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5-溴-1-戊烯 在 Zeise's dimer 碘 、 magnesium 、 三(4-三氟甲苯基)膦 作用下， 以 四氢呋喃 、 1,1,2,2-四氯乙烷 为溶剂， 反应 10.0h， 生成 (+/-)-(2R,6R)-2-benzyl-6-methyltetrahydro-2H-pyran
  参考文献：
  名称：

  铂催化γ-和δ-羟基烯烃的分子内氢烷氧基化形成环醚

  摘要：

  2,2-二苯基-4-戊烯-1-醇与 [PtCl2(H2CCH2)]2 (1 mol %) 和 P(4-C6H4CF3)3 (2 mol %) 的催化混合物在 70 °C 下反应24 小时导致以 78% 的产率分离出 2-甲基-4,4-二苯基四氢呋喃。γ-羟基烯烃的铂催化加氢烷氧基化容许在 α、β 和 γ-碳原子以及内部和顺式和反式末端烯烃位置发生取代。铂催化的加氢烷氧基化耐受许多官能团，包括新戊酸酯和乙酸酯、酰胺、甲硅烷基和苄基醚，以及侧羟基和烯烃基团。Pt催化的烯烃加氢烷基化也适用于稠合和螺双环醚的形成，并且对δ-羟基烯烃的加氢烷氧基化形成四氢吡喃衍生物是有效的。

  DOI：

  10.1021/ja0477773

文献信息

• Stereoselective Construction of Cyclic Ethers Using a Tandem Two-Component Etherification:  Elucidation of the Role of Bismuth Tribromide
  作者：P. Andrew Evans、Jian Cui、Santosh J. Gharpure、Robert J. Hinkle

  DOI：10.1021/ja036439j

  日期：2003.9.1

  important area of synthetic interest, particularly given the ubiquity of C-glycoside derivatives in natural and unnatural pharmacologically important agents. This work describes a series of intramolecular etherification reactions of delta-trialkylsilyloxy aldehydes and ketones using catalytic bismuth tribromide and various trialkylsilyl nucleophiles for the construction of cis- and trans-2,6-di- and trisubstituted

  环醚的立体发散结构仍然是一个重要的合成领域，特别是考虑到 C-糖苷衍生物在天然和非天然的药理学重要试剂中普遍存在。这项工作描述了一系列 δ-三烷基甲硅烷氧基醛和酮的分子内醚化反应，使用催化三溴化铋和各种三烷基甲硅烷基亲核试剂来构建顺式和反式 2,6-二和三取代的四氢吡喃。此外，这项研究提供了令人信服的证据，证明催化作用可能归因于三溴化铋水解产生的溴化氢和溴氧化铋。
• Stereoselective Construction of <i>cis</i>-2,6-Disubstituted Tetrahydropyrans <i>via</i> the Reductive Etherification of δ-Trialkylsilyloxy Substituted Ketones:  Total Synthesis of (−)-Centrolobine
  作者：P. Andrew Evans、Jian Cui、Santosh J. Gharpure

  DOI：10.1021/ol035438t

  日期：2003.10.1

  [reaction: see text] The stereoselective intramolecular reductive etherification of delta-trialkylsilyloxy substituted ketones with catalytic bismuth tribromide and triethylsilane provides a convenient method for the construction of cis-2,6-disubstituted tetrahydropyrans. This method was highlighted in the key step of an expeditious total synthesis of the antibiotic, (-)-centrolobine.

  [反应：见正文]δ-三烷基甲硅烷氧基取代的酮与催化三溴化铋和三乙基硅烷的立体选择性分子内还原醚化为构建cis-2,6-二取代的四氢吡喃提供了一种方便的方法。快速合成抗生素（-）-centrolobine的关键步骤突显了该方法。
• Multicatalytic Synthesis of Complex Tetrahydrofurans Involving Bismuth(III) Triflate Catalyzed Intramolecular Hydroalkoxylation of Unactivated Olefins
  作者：Brendan D. Kelly、Julia M. Allen、Rachel E. Tundel、Tristan H. Lambert

  DOI：10.1021/ol900198r

  日期：2009.3.19

  A multicatalytic synthesis of complex tetrahydrofurans has been developed involving a Bi(OTf)(3)-Catalyzed nucleophilic addition/hydroalkoxylation sequence. Complex tetrahydrofuranyl products may be formed rapidly in high yield and with good diastereoselectivity. The demonstrated scope of hydroalkoxylation has also been expanded to include substrates bearing useful functional handles including carboxylate ester, olefin, nitrile, and nitro groups.
• Titanium-mediated carbonyl olefinations. 2. Benzylidenations of carbonyl compounds with dibenzyl titanocene
  作者：Nicos A. Petasis、Eugene I. Bzowej

  DOI：10.1021/jo00031a006

  日期：1992.2

  Mild thermolysis of carbonyl compounds with dibenzyltitanocene affords phenyl-substituted olefins, enol ethers, and enamines.
• On the choice of Lewis acids for the Prins reaction; two total syntheses of (±)-Civet
  作者：Freda K. Chio、Julie Warne、Damien Gough、Mark Penny、Sasa Green (née Martinović)、Simon J. Coles、Mike B. Hursthouse、Peter Jones、Lorraine Hassall、Thomas M. McGuire、Adrian P. Dobbs

  DOI：10.1016/j.tet.2011.05.019

  日期：2011.7

  While developing new variations of the Prins cyclisation reaction, the effect of the choice of Lewis acid on the outcome of the reaction and the product(s) has been investigated, yielding hitherto unseen dihydropyran products in the Prins cyclisation reaction of homoallylic alcohols, and two new modifications of the reaction: the triflate-trapped Prins adduct and the Mukaiyama-Aldol-silyl-Prins reaction. Two of these methods are employed in two complementary total syntheses of the important perfumery compound, (+/-)-Civet. (C) 2011 Elsevier Ltd. All rights reserved.