(2R,3R,5S)-3-benzoyloxy-5-bromomethyl-2-methyltetrahydrofuran | 632330-48-4

• 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: (2R,3R,5S)-3-benzoyloxy-5-bromomethyl-2-methyltetrahydrofuran
• 英文别名: trans-3-benzoyloxy-5-bromomethyl-trans-2-methyltetrahydrofuran；[(2R,3R,5S)-5-(bromomethyl)-2-methyloxolan-3-yl] benzoate
• CAS: 632330-48-4
• 化学式: C₁₃H₁₅BrO₃
• 分子量: 299.164
• InChiKey: HHRGZSXPJYISAF-ADEWGFFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R,5S)-3-benzoyloxy-5-bromomethyl-2-methyltetrahydrofuran 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以78%的产率得到(2R,3R,5S)-5-bromomethyl-2-methyltetrahydrofuran-3-ol
  参考文献：
  名称：

  Synthesis of enantiopure (2R)-configured muscarine alkaloids via selective alkoxyl radical ring-closure reactions

  摘要：

  A new synthesis of (-)-muscarine, (+)-allo-muscarine, (-)-epi-muscarine, and (-)-epiallo-muscarine has been devised which utilizes selective alkoxyl radical cyclizations for constructing tri-substituted tetrahydrofuran units. Photolysis of (2R,3S)-N-(3-benzoyloxy-5-hexen-2-oxy)-4-methylthiazole-2(3H)thione in the presence of BrCCl3 provided (2R,3S,5S)-3-benzoyloxy-5-broniomethyl-2-methyltetrahydrofuran as the major product and the corresponding (2R,3S,5R)-isomer as the minor. These building blocks were converted into enantiomerically pure (+)-allo-muscarine (from the major alkoxyl radical cyclization product) and (-)-muscarine (from the minor product). Temperature and substituent effects on the diastereoselectivity of the underlying alkoxyl radical cyclization have been investigated. (-)-epi-Muscarine and (-)-epiallo-muscarine have been prepared likewise, starting from (2R.3R)-ev-(3-benzoyloxy-5-hexen-2-oxy)-4-metliylthiazole-2(3H)thione. (C) 2003 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2003.06.006
• 作为产物：
  描述：

  (2S,3R)-3-benzoyloxy-5-hexen-2-yl p-toluenesulfonate 在 三氯溴甲烷 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 120.42h， 生成 (2R,3R,5S)-3-benzoyloxy-5-bromomethyl-2-methyltetrahydrofuran
  参考文献：
  名称：

  Synthesis of enantiopure (2R)-configured muscarine alkaloids via selective alkoxyl radical ring-closure reactions

  摘要：

  A new synthesis of (-)-muscarine, (+)-allo-muscarine, (-)-epi-muscarine, and (-)-epiallo-muscarine has been devised which utilizes selective alkoxyl radical cyclizations for constructing tri-substituted tetrahydrofuran units. Photolysis of (2R,3S)-N-(3-benzoyloxy-5-hexen-2-oxy)-4-methylthiazole-2(3H)thione in the presence of BrCCl3 provided (2R,3S,5S)-3-benzoyloxy-5-broniomethyl-2-methyltetrahydrofuran as the major product and the corresponding (2R,3S,5R)-isomer as the minor. These building blocks were converted into enantiomerically pure (+)-allo-muscarine (from the major alkoxyl radical cyclization product) and (-)-muscarine (from the minor product). Temperature and substituent effects on the diastereoselectivity of the underlying alkoxyl radical cyclization have been investigated. (-)-epi-Muscarine and (-)-epiallo-muscarine have been prepared likewise, starting from (2R.3R)-ev-(3-benzoyloxy-5-hexen-2-oxy)-4-metliylthiazole-2(3H)thione. (C) 2003 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2003.06.006

文献信息

• Ring Closure Reactions of Disubstituted 4-Penten-1-oxyl Radicals − Towards a Stereoselective Synthesis ofallo-Muscarine
  作者：Jens Hartung、Rainer Kneuer

  DOI：10.1002/(sici)1099-0690(200005)2000:9<1677::aid-ejoc1677>3.0.co;2-x

  日期：2000.5

  tetrahydrofurans was achieved by an efficient and highly regioselective alkoxyl radical cyclization (5-exo-trig). The 2,3-anti substituted intermediates 9 and 12 cyclize stereoselectively whereas a 2,3-syn-configured O-radical affords both possible diastereomeric addition products in equal amounts. The cyclized tetrahydrofuryl methyl radicals were trapped with the bromine atom donor BrCCl3 to afford the bromomethyl-substituted

  三取代的官能四氢呋喃10，11，16，18，和19分别从光化学制备2,3-顺式-和2,3-反-型ñ - （3-苯甲酰基-5-己烯-2-氧基）噻唑-2- （3 ħ） -硫酮抗- 6，pyridinethiones 7，抗- 8，和BrCCl 3。四氢呋喃的形成通过有效且高度区域选择性的烷氧基自由基环化（5- exo -trig）实现。2,3-抗被取代的中间体9和12立体选择性地环化，而2，3-顺式构型的O-自由基提供相等量的两种可能的非对映异构加成产物。该环化的四氢呋喃基甲基自由基被困与溴原子供体BrCCl 3，得到溴甲基取代的环醚10，11，18，和19以优良产率。-该反应的效用通过在两步合成为（+）的新制备的四氢呋喃中的一个的转换强调异体-muscarine（+） - 20。