(1R,2R,3r,4S,5S)-3-methoxy-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene | 146821-16-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1R,2R,3r,4S,5S)-3-methoxy-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene
• CAS: 146821-16-1
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: FKBHQOWSVJSBTF-JEDPFWTOSA-N

物化性质

• 沸点：
  214.5±40.0 °C(predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.61
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,3r,4S,5S)-3-methoxy-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene 在 硫酸 、 碳酸氢钠 、 间氯过氧苯甲酸 、 (+)-二异松蒎烯基硼烷 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 168.0h， 生成 methyl 2-[(2S,3R,4R,5R,6R)-4,6-dimethoxy-3,5-dimethyloxan-2-yl]acetate
  参考文献：
  名称：

  A formal total synthesis of crocacin C

  摘要：

  An efficient total synthesis of a potent antifungal and moderate cytotoxic agent crocacin C is described. The synthesis involves the generation of four contiguous stereogenic centres via desymmetrization of a meso bicyclic dihydrofuran using asymmetric hydroboration. (c) 2006 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2006.10.141
• 作为产物：
  描述：

  (1R,2S,4R,5S)-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-one 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 20.25h， 生成 (1R,2R,3r,4S,5S)-3-methoxy-2,4-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene
  参考文献：
  名称：

  Almeida Barbosa, Luiz-Claudio de; Culter, David; Mann, John, Journal of the Chemical Society. Perkin transactions I, 1996, # 11, p. 1101 - 1106

  摘要：

  DOI：

文献信息

• Enantioselective Enzymatic Desymmetrization of Highly Functionalized <i>Meso</i> Tetrahydropyranyl Diols
  作者：Mathieu Candy、Gérard Audran、Hugues Bienaymé、Cyril Bressy、Jean-Marc Pons

  DOI：10.1021/ol902107g

  日期：2009.11.5

  The enantioselective enzymatic desymmetrization of several highly substituted meso-tetrahydropyranyl diols is described. This transformation leads to valuable building blocks containing up to five stereogenic centers, which are revealed in a single step with both high yields and excellent enantiomeric excesses. Moreover, it was shown that this kind of building blocks could provide an easy access to

  描述了几种高度取代的内消旋-四氢吡喃基二醇的对映选择性酶促不对称化。这种转化导致了有价值的结构单元，其中包含多达五个立体异构中心，这些一步一步即可揭示，同时具有高收率和出色的对映异构体过量。而且，已经表明，这种结构单元可以容易地获得高度官能化的立体四链体的两种对映异构体。
• Iron-Catalyzed Regio- and Stereoselective Ring Opening of [2.2.1]- and [3.2.1]Oxabicyclic Alkenes with a Grignard Reagent
  作者：Masaharu Nakamura、Keiko Matsuo、Toshihiro Inoue、Eiichi Nakamura

  DOI：10.1021/ol034375b

  日期：2003.4.1

  [reaction: see text] Arylative and alkenylative ring-opening reactions of a [2.2.1]- or [3.2.1]oxabicyclic alkene with a Grignard reagent take place in the presence of a catalytic amount of iron(III) chloride and a stoichiometric amount of TMEDA to produce a highly substituted 3-cyclohexen-1-ol or 3-cyclohepten-1-ol in good yield with high regio- and stereoselectivity.

  [反应：参见正文] [2.2.1]-或[3.2.1]氧杂双环烯烃与格利雅试剂的芳基和烯基开环反应是在催化量的氯化铁（III）和氯化氢存在下进行的。化学计量的TMEDA量，可产生高取代度的3-环己烯-1-醇或3-环庚烯-1-醇，并具有较高的区域选择性和立体选择性。
• Metal-catalyzed cyclopropanation on the 8-oxabicyclo[3.2.1]oct-6-ene template
  作者：Sze-Kar Leung、Pauline Chiu

  DOI：10.1016/j.tetlet.2005.01.182

  日期：2005.4

  Cyclopropanations of an 8-oxabicyclo[3.2.1]octene substrate using diazocarbonyl compounds provided exo, exo-cyclo-propanated products as the sole or major diastereomeric oxatricyclic products. Reductive cleavage of a meso-oxatricyclic ketone by samarium iodide resulted in desymmetrization without concomitant oxygen bridge cleavage. (c) 2005 Elsevier Ltd. All rights reserved.
• Total Synthesis of (+)-Crocacin C Using Hidden Symmetry
  作者：Mathieu Candy、Gérard Audran、Hugues Bienaymé、Cyril Bressy、Jean-Marc Pons

  DOI：10.1021/jo902582w

  日期：2010.3.5

  A highly convergent and protecting-group-free synthesis of (+)-crocacin C, featuring an enzymatic enantioselective desymmetrization of a meso-diol, a base-induced ring opening of a THP ring, and a one-pot hydrostannylation/Stille coupling as the key steps, is reported. The natural product was obtained in 11 steps and 22.3% overall yield starting from readily available oxabicycle 1. Finally, a unique enantioselective step, an enzymatic desymmetrization, revealed four stereogenic centers and created one in C4 of the THP furnishing the dense building block 4 with high enantioselectivity (ce >98%).