(3RS,4RS)-cis-4-Benzyl-3-hydroxytetrahydrofuran

• 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: (3RS,4RS)-cis-4-Benzyl-3-hydroxytetrahydrofuran
• 英文别名: cis-3-hydroxy-4-(phenylmethyl)tetrahydrofuran；(3S,4S)-4-benzyloxolan-3-ol
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: DBSHHWVKURKFCT-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3RS,4RS)-cis-4-Benzyl-3-hydroxytetrahydrofuran 在 W-2 Ra-Ni 正丁基锂 、 甲基锂 作用下， 以 乙醇 为溶剂， 反应 42.0h， 生成 (3R,4R)-3,4-Dibenzyltetrahydrofuran
  参考文献：
  名称：

  Enantiocontrolled synthesis of burseran, brassilignan, dehydroxycubebin, and other tetrahydrofuran lignans in both enantiomeric forms. Application of intermolecular nitrile oxide cycloadditions and lipase-mediated kinetic resolutions

  摘要：

  Several natural and unnatural tetrahydrofuran lignans have been synthesized by a convergent approach. Our methodology utilizes a nitrile oxide cycloaddition to dihydrofuran 8 and an enzymatic resolution of alcohols 11 by lipase PS. The lipase-mediated kinetic resolution of alcohols 11 furnished both enantiomers of the lignan precursors 12 and 14 in high optical purity (>99% ee). This is followed by a S(N)2 displacement of tosylates 15 and 18 by alpha-lithiobenzyl phenyl sulfides. In this manner, both enantiomers of 3,4-dibenzyltetrahydrofuran (17a, 20a), 3,4-bis(3-methoxybenzyl)-tetrahydrofuran (17b, 20b), brassilignan (17c, 20c), dehydroxycubebin (17d, 20d), and burseran (17e, 20e) were synthesized in overall yields of 6-16%.

  DOI：

  10.1021/jo00060a037
• 作为产物：
  描述：

  cis-3-benzoyl-4-hydroxytetrahydrofuran 在 palladium on activated charcoal 硫酸 、 氢气 、 potassium carbonate 作用下， 以 甲醇 、 水 为溶剂， 反应 13.0h， 生成 (3RS,4RS)-cis-4-Benzyl-3-hydroxytetrahydrofuran
  参考文献：
  名称：

  Enantiocontrolled synthesis of burseran, brassilignan, dehydroxycubebin, and other tetrahydrofuran lignans in both enantiomeric forms. Application of intermolecular nitrile oxide cycloadditions and lipase-mediated kinetic resolutions

  摘要：

  Several natural and unnatural tetrahydrofuran lignans have been synthesized by a convergent approach. Our methodology utilizes a nitrile oxide cycloaddition to dihydrofuran 8 and an enzymatic resolution of alcohols 11 by lipase PS. The lipase-mediated kinetic resolution of alcohols 11 furnished both enantiomers of the lignan precursors 12 and 14 in high optical purity (>99% ee). This is followed by a S(N)2 displacement of tosylates 15 and 18 by alpha-lithiobenzyl phenyl sulfides. In this manner, both enantiomers of 3,4-dibenzyltetrahydrofuran (17a, 20a), 3,4-bis(3-methoxybenzyl)-tetrahydrofuran (17b, 20b), brassilignan (17c, 20c), dehydroxycubebin (17d, 20d), and burseran (17e, 20e) were synthesized in overall yields of 6-16%.

  DOI：

  10.1021/jo00060a037

文献信息

• Preparation of Polycyclic Systems by Sequential 5-<i>E</i><i>xo</i>-<i>D</i><i>igonal</i> Radical Cyclization, 1,5-Hydrogen Transfer from Silicon, and 5-<i>E</i><i>ndo</i>-<i>T</i><i>rigonal</i> Cyclization
  作者：Derrick L. J. Clive、Wen Yang、Aaron C. MacDonald、Zhongren Wang、Michel Cantin

  DOI：10.1021/jo001124x

  日期：2001.3.1

  diagonal cyclization, and the resulting vinyl radical abstracts hydrogen from silicon to afford a silicon-centered radical. This radical closes in a 5-endo trigonal manner to generate radicals of type 4, which are reduced (4 --> 5) by stannane, except when the starting acetylene carries a terminal trimethylstannyl group. In this case, radicals 4 expel trimethylstannyl radical to afford vinyl silanes

  类型1的基团经历5-exo对角环化，并且所得的乙烯基自由基从硅中提取氢以提供以硅为中心的自由基。该自由基以5-内三角键关闭，生成4型自由基，该自由基被锡烷还原（4-> 5），除非起始乙炔带有末端三甲基锡烷基。在这种情况下，自由基4排出三甲基锡烷基以提供乙烯基硅烷6。自由基级联1→5的立体化学结果受1中含氧碳的立体化学控制（请参阅加星标的原子）。该序列可以由碳，α-取代的碳，氧酰基和氨基甲酰基基团起始，并产生稠合到碳环或杂环上的含硅环。描述了许多示例，