cis-4-methyl-2-phenyltetrahydrofuran | 38300-00-4

• 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: cis-4-methyl-2-phenyltetrahydrofuran
• 英文别名: cis-3-methyl-5-phenyloxolane；(2R,4R)-4-Methyl-2-phenyloxolane
• CAS: 38300-00-4
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: UOJBMAVYSVZFMX-MWLCHTKSSA-N

物化性质

• 沸点：
  245.1±19.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  1-苯基-3-丁烯-1-醇 在 正丁基锂 、 偶氮二异丁腈 、 三乙基硼 、 三正丁基氢锡 、 sodium hydride 作用下， 以 甲苯 为溶剂， 反应 0.33h， 生成 cis-4-methyl-2-phenyltetrahydrofuran
  参考文献：
  名称：

  Scope of alkoxymethyl radical cyclizations

  摘要：

  We have explored different aspects of the cyclization capability of alkoxymethyl radicals and report here a full account of our investigations. The required radicals were generated from (phenylseleno)methyl ethers (e.g., 6), which were prepared from homoallylic or bis-homoallylic alcohols by a two-step process. The alcohols were alkylated with (iodomethyl)tributylstannane. The stannanes were reacted with n-BuLi, and the resulting alpha-alkoxyanions were trapped with diphenyldiselenide to give the (phenylseleno)methyl ethers, which were stable to chromatography. When treated with tributyltin hydride, in the presence of a radical initiator, these precursors undergo a smooth cyclization to substituted tetrahydrofurans and tetrahydropyrans. Formation of the cyclization product was found to be the primary pathway even at relatively high tin hydride concentration. The diastereoselectivity of this cyclization was comparable to that observed in other radical cyclizations. The cis selectivity in cyclization of 6 increased gradually (up to 11:1) as the reaction temperature was lowered. The cyclization can be used for the synthesis of bicyclic and tricyclic compounds and can be incorporated in systems capable of tandem cyclizations.

  DOI：

  10.1021/jo00079a016

文献信息

• Inter- and Intramolecular Radical Couplings of Ene-ynes or Halo-alkenes Promoted by an InCl₃/MeONa/Ph₂SiH₂ System
  作者：Naoki Hayashi、Ikuya Shibata、Akio Baba

  DOI：10.1021/ol051114o

  日期：2005.7.1

  (HInCl(2)) under nonacidic conditions is achieved by transmetalation between Ph(2)SiH(2) and InCl(2)OMe. The presented system achieves the titled coupling reactions in a radical manner. In particular, the nonacidic character enables the applications to acid-sensitive inter- and intramolecular ene-yne couplings.

  [反应：见正文]通过在Ph（2）SiH（2）和InCl（2）OMe之间进行金属转移，可在非酸性条件下有效生成氢化铟（HInCl（2））。所提出的系统以根本的方式实现了标题的偶联反应。特别地，非酸性特征使得能够应用于对酸敏感的分子间和分子内烯-炔偶联。
• Homogeneous sonochemistry in radical-chain reactions. Sonochemical hydrostannation and tin hydride reduction
  作者：Eiichi Nakamura、Daisuke Machii、Tsuyoshi Inubushi

  DOI：10.1021/ja00199a059

  日期：1989.8

  sonochemistry for the controlled initiation of radical chain reactions: radicals generated undergo chain reactions in the bulk medium in such a way that the low concentration of the initial radical species may be compensated by the length of the chain. We report here the first synthetic application of this concept by describing hydrostannation and tin hydride reduction initiated by sonochemical thermolysis of

  我们已经研究了用于受控引发自由基链反应的均相声化学：产生的自由基在大量介质中进行链反应，初始自由基物种的低浓度可以通过链的长度来补偿。我们通过描述由 R 3 SnH 的声化学热解引发的氢化锡化和氢化锡还原，在这里报告了这一概念的首次合成应用
• Lewis Acid Mediated “<i>endo-dig</i>” Hydroalkoxylation–Reduction on Internal Alkynols for the Stereoselective Synthesis of Cyclic Ethers and 1,4-Oxazepanes
  作者：Santosh J. Gharpure、Dharmendra S. Vishwakarma、Santosh K. Nanda

  DOI：10.1021/acs.orglett.7b03241

  日期：2017.12.15

  Lewis acid mediated 5/6/7-endo-dig hydroalkoxylation–reduction cascade on internal alkynols gave an expedient, stereoselective synthesis of cyclic ethers and 1,4-oxazepanes. The strategy has been extended to the first examples of hydroalkoxylation–alkyne Prins-type cyclization cascade of alkyne-tethered alkynols, giving access to oxa-bicyclic scaffolds. This method was used as the key step in the stereoselective

  路易斯酸介导的5/6 / 7-内切挖内部炔醇hydroalkoxylation还原级联得到一个有利的，环醚和1,4- oxazep​​anes的立体选择性合成。该策略已扩展到炔烃系链炔​​醇的加氢烷氧基化-炔烃Prins型环化级联的第一个实例，从而可以使用氧杂双环骨架。该方法被用作花环烷AB以及（±）-中心洛宾及其同系物的立​​体选择性全合成中的关键步骤。
• Radical-Triggered Three-Component Coupling Reaction of Alkenylboronates, α-Halocarbonyl Compounds, and Organolithium Reagents: The Inverse Ylid Mechanism
  作者：Nicholas D. C. Tappin、Manuel Gnägi-Lux、Philippe Renaud

  DOI：10.1002/chem.201802384

  日期：2018.8.6

  An operationally simple protocol to affect a radical addition to alkenylboronates that spontaneously undergo a [1,2]‐metalate shift is described. Overall, the reaction is a three‐component coupling of an organolithium, alkenylboronic ester, and halide which takes place with broad scope and good to excellent yields. Experimental mechanistic investigations support the formation of a boron inverse ylid

  描述了一种操作简单的方案，可影响自由基自发地发生[1,2]-金属酸盐转变的链烯基硼酸酯的加成反应。总体而言，该反应是有机锂，烯基硼酸酯和卤化物的三组分偶合，反应范围广，收率好至极好。实验机制的研究支持形成硼逆碘中间体。
• Tetrahydrofuran Derivatives from Epoxides <i>via</i> Group Transfer Cyclization or Reductive Radical Cyclization of Organotellurium and Organoselenium Intermediates
  作者：Lars Engman、Vijay Gupta

  DOI：10.1021/jo961578n

  日期：1997.1.1

  undergo group transfer cyclization to afford 2-substituted 4-[(aryltelluro)methyl]tetrahydrofurans (cis/trans = 1/3-1/10). The aryl beta-(prop-2-ynyloxy)alkyl tellurides similarly afforded 2-substituted 4-[(aryltelluro)methylene]tetrahydrofurans with an E/Z-ratio close to unity. The beta-(allyloxy)alkyl aryl selenides and aryl beta-(prop-2-ynyloxy)alkyl selenides failed to undergo group transfer cyclization

  单取代的环氧化物从空间上受阻最小的一面通过苯碲酸根和苯硒酸根试剂进行区域特异性开环，分别得到芳基β-羟烷基碲化物和硒化物。通过在四氢呋喃中用烯丙基溴/氢化钠处理将这些材料进行O-烯丙基化，并在与炔丙基溴/氢化钠反应时将O-prop-2-炔化。在含有40 mol％的六丁基二锡的苯中进行光解后，发现β-（烯丙氧基）烷基芳基碲化物经历了基团转移环化，从而获得了2-取代的4-[（（芳基碲基）甲基]四氢呋喃（顺式/反式= 1 / 3- 1/10）。芳基β-（丙-2-炔氧基）烷基碲化物类似地得到E / Z比接近于1的2-取代的4-[（芳基碲基）亚甲基]四氢呋喃。β-（烯丙氧基）烷基芳基硒化物和芳基β-（丙-2-基氧基氧基）烷基硒化物未进行基团转移环化。在氢化三丁基锡和2,2'-偶氮二异丁腈的存在下，发现前一种化合物以高收率进行还原性自由基环化，得到2-取代的4-甲基四氢呋喃（顺式/反式= 1 / 3-1