(1R,3R,4R,6R,8R,12R)-12-bromo-6-methoxy-3,4-diphenyl-2,5-dioxabicyclo[6.4.0]dodec-9-ene | 464184-42-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (1R,3R,4R,6R,8R,12R)-12-bromo-6-methoxy-3,4-diphenyl-2,5-dioxabicyclo[6.4.0]dodec-9-ene
• 英文别名: (2R,3R,5R,6aR,10R,10aR)-10-bromo-5-methoxy-2,3-diphenyl-2,3,5,6,6a,9,10,10a-octahydro-1,4-benzodioxocine
• CAS: 464184-42-7
• 化学式: C₂₃H₂₅BrO₃
• 分子量: 429.354
• InChiKey: IMMAQRLRIIXLAQ-BEWOIHDRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,3R,4R,6R,8R,12R)-12-bromo-6-methoxy-3,4-diphenyl-2,5-dioxabicyclo[6.4.0]dodec-9-ene 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以89%的产率得到(1S,3R,4R,6R,8R)-6-methoxy-3,4-diphenyl-2,5-dioxabicyclo[6.4.0]dodec-9-ene
  参考文献：
  名称：

  简洁的不对称全合成鞘磷脂，一种有效的中性鞘磷脂酶抑制剂。

  摘要：

  通过缩合旋光性环己烷单元（由我们自己的方法由市售1,4-环己二烯制备）和侧链（由Hoye和Tennakoon（TR Hoye，MA Tennakoon，Org.Lett.2000，2，1481-1483）。环氧环己烯酮单元的修饰是在总合成的后期完成的，伯醇的脱保护是在最后一步进行的。在合成过程中，获得了几个关键的反应：1）环己二烯缩醛的分子内溴醚化； 2）环己二烯缩醛的分子内溴醚化。2）立体选择性地引入叔醇，3）与三氟甲磺酸硅酯/ 2,4结合使乙缩醛官能团与醛脱保护，从二羟基乙缩醛化合物中6-可力丁和一锅合成具有不同甲硅烷基基团的二甲硅烷基醛化合物；4）伯醇的2，4-二甲氧基苯基甲基（（2，4）DMPM）保护基的容易的脱保护。

  DOI：

  10.1002/chem.200700871
• 作为产物：
  描述：

  cyclohexa-2,5-dienylethanal diethylacetal 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 乙腈 为溶剂， 生成 (1R,3R,4R,6R,8R,12R)-12-bromo-6-methoxy-3,4-diphenyl-2,5-dioxabicyclo[6.4.0]dodec-9-ene
  参考文献：
  名称：

  鞘脂抑素的环己烯酮核心的模型化合物（4 S，5 S，6 S）-6-（2,2-二甲氧基）乙基-4,5-环氧-6-羟基-2-环己烯酮的简明不对称合成

  摘要：

  光学纯度的环己汀（1）的环己烯酮核心是由环己二烯缩醛5合成的。在最终步骤中，我们合成的关键方面包括分子内溴醚化5，SeO 2氧化7和烯酮形成13至4。

  DOI：

  10.1016/s0040-4039(02)00916-4

文献信息

• New Perspective for Natural Products Synthesis:  Concise Synthesis of (+)-Sch 642305 by Chiral Auxiliary Multiuse Methodology
  作者：Hiromichi Fujioka、Yusuke Ohba、Kenji Nakahara、Mayuko Takatsuji、Kenichi Murai、Motoki Ito、Yasuyuki Kita

  DOI：10.1021/ol702530b

  日期：2007.12.1

  The synthesis of (+)-Sch 642305 is an example of chiral auxiliary multiuse methodology, which shows a new perspective for the synthesis of compounds with multiple asymmetric centers. Thus, (+)-Sch 642305 was concisely synthesized from the known compound. Every reaction is stereoselective, and the chiral nonracemic hydrobenzoin worked as chiral auxiliary for desymmetrization of diene, as a template for

  （+）-Sch 642305的合成是手性辅助多用途方法的一个例子，它为合成具有多个不对称中心的化合物显示了新的视角。因此，从已知化合物简明地合成了（+）-Sch 642305。每个反应都是立体选择性的，手性非外消旋氢安息香用作二烯脱对称的手性助剂，是实现区域和立体选择性反应的模板，是C4位的氧源，并且是羟基官能团的保护基。即，手性助剂在整个合成的每个步骤中都起作用。此外，该合成包含用于获得α'-烷基化烯酮化合物的新方案。
• Mild and Efficient Removal of Hydroxyethyl Unit from 2-Hydroxyethyl Ether Derivatives Leading to Alcohols
  作者：Hiromichi Fujioka、Yusuke Ohba、Hideki Hirose、Kenichi Murai、Yasuyuki Kita

  DOI：10.1021/ol051135i

  日期：2005.7.1

  CAN is a good reagent for the transformation of 2-hydroxyethyl ether units to alcohols. Significantly, many functional groups can tolerate the reaction conditions, although they do not survive under many previously reported removal conditions. The reaction mechanism is clarified.
• Cerium ammonium nitrate (CAN) for mild and efficient reagent to remove hydroxyethyl units from 2-hydroxyethyl ethers and 2-hydroxyethyl amines
  作者：Hiromichi Fujioka、Hideki Hirose、Yusuke Ohba、Kenichi Murai、Kenji Nakahara、Yasuyuki Kita

  DOI：10.1016/j.tet.2006.11.004

  日期：2007.1

  Cerium ammonium nitrate (CAN) removed hydroxyethyl units from 2-hydroxyethyl ethers and 2-hydroxyethyl amines to produce alcohols and amines in good yields. Especially, removal of the 2-hydroxyethyl ethers from C-2-symmetric diols, chiral 2,3-butanediol and chiral hydrobenzoin, was very useful for asymmetric syntheses using C-2-symmetric diols. The reactions using dual abilities of CAN, i.e., the ability for removal of the 2-hydroxyethyl unit and the ability for acetal hydrolysis by a single electron transfer, were also achieved Successfully. The reaction conditions were very mild and efficient, and many functional groups, which can be affected under normal conditions, were unaffected during the reaction. (c) 2006 Published by Elsevier Ltd.
• The first asymmetric total syntheses of both enantiomers of cryptocaryone
  作者：Hiromichi Fujioka、Kenji Nakahara、Tomohiro Oki、Kie Hirano、Tatsuya Hayashi、Yasuyuki Kita

  DOI：10.1016/j.tetlet.2010.01.101

  日期：2010.4

  The first asymmetric total syntheses of the (+)- and (-)-cryptocaryones are described. Removal of the acetal unit of the enone acetal 5, which was obtained in our previous study from the cyclohexadiene acetal 3, afforded the enone acetal 8 in a one-pot procedure. The acylation of 8 with cinnamoyl chloride and subsequent hydrolysis of the resulting acetal gave the lactol 11. Its oxidation with NIS and tetra-n-butyl-ammonium iodide (TBAI) finally furnished the natural (+)-cryptocaryone 2. The same procedure from ent-3 afforded the unnatural one 1. (C) 2010 Elsevier Ltd. All rights reserved.
• Concise asymmetric synthesis of a model compound, (4S,5S,6S)-6-(2,2-dimethoxy)ethyl-4,5-epoxy-6-hydroxy-2-cyclohexenone, for the cyclohexenone core of scyphostatin
  作者：Hiromichi Fujioka、Naoyuki Kotoku、Yoshinari Sawama、Yasushi Nagatomi、Yasuyuki Kita

  DOI：10.1016/s0040-4039(02)00916-4

  日期：2002.7

  The optically pure cyclohexenone core of scyphostatin (1) has been synthesized from cyclohexadiene acetal 5. The crucial aspects of our synthesis include the intramolecular bromoetherification of 5, the SeO2 oxidation of 7, and the enone formation of 13 to 4 in the final step.

  光学纯度的环己汀（1）的环己烯酮核心是由环己二烯缩醛5合成的。在最终步骤中，我们合成的关键方面包括分子内溴醚化5，SeO 2氧化7和烯酮形成13至4。