(+)-9-bromo-2R-tert-butyl-1,4-dioxaspiro[4.(5R)]deca-7,9-dien-6-one | 1038436-93-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-9-bromo-2R-tert-butyl-1,4-dioxaspiro[4.(5R)]deca-7,9-dien-6-one
• 英文别名: (3R,5R)-9-bromo-3-tert-butyl-1,4-dioxaspiro[4.5]deca-7,9-dien-6-one
• CAS: 1038436-93-9
• 化学式: C₁₂H₁₅BrO₃
• 分子量: 287.153
• InChiKey: YIVZWIDPUUTQQR-CMPLNLGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 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：

  (+)-9-bromo-2R-tert-butyl-1,4-dioxaspiro[4.(5R)]deca-7,9-dien-6-one 在 盐酸 、 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 水 为溶剂， 反应 6.5h， 生成 9-bromo-(2R)-tert-butyl-7,8-dihydroxy-(6S)-methyl-1,4-dioxaspiro[4.(5R)]dec-9-en-6-ol.
  参考文献：
  名称：

  通过高价碘介导的苯酚脱芳香化反应合成Sphophostatin类似物

  摘要：

  从容易获得的邻位取代的酚类可实现两种鞘磷脂抑制素类似物的简明合成。主要功能包括通过手性沙仑型双（λ促进不对称和仿生hydroxylative苯酚脱芳构化（HPD）反应5 -iodane）试剂，接着是在原位区域选择性和diastereocontrolled环氧化。

  DOI：

  10.1021/acs.joc.7b02366
• 作为产物：
  描述：

  (+)-2-[(R)-2-hydroxy-3,3-dimethylbutoxy]-4-bromophenol 在 碘苯二乙酸 、 碳酸氢钠 作用下， 以 2,2,2-三氟乙醇 为溶剂， 反应 0.58h， 生成 (+)-9-bromo-2R-tert-butyl-1,4-dioxaspiro[4.(5R)]deca-7,9-dien-6-one
  参考文献：
  名称：

  通过λ3-碘介导的酚类氧化脱芳香化反应，高非对映选择性合成邻醌单缩酮。

  摘要：

  DOI：

  10.1002/anie.200705816

文献信息

• Hypervalent iodine-mediated oxygenative phenol dearomatization reactions
  作者：Laurent Pouységu、Tahiri Sylla、Tony Garnier、Luis B. Rojas、Jaime Charris、Denis Deffieux、Stéphane Quideau

  DOI：10.1016/j.tet.2010.05.078

  日期：2010.7

  Both lambda(3)- and lambda(5)-iodanes have proven to be useful reagents in the oxygenative dearomatization of phenols, and exploitations of their chemistry in the conception of both substrate- and reagent-controlled asymmetric variants of such a transformation of great value for natural product synthesis have shown evident signs of success. Moreover, the use of stabilized IBX (i.e., SIBX) in our methodology for O-demethylation of 2-methoxyphenols, which relies on the same key oxygenating dearomatization event, is reported here to be much more efficacious than that of 1BX itself in the chemoselective one-step conversion of homovanillyl alcohol into hydroxytyrosol, and bergenin into norbergenin. (C) 2010 Elsevier Ltd. All rights reserved.
• Regio- and stereoselectivities in Diels–Alder cyclodimerizations of orthoquinonoid cyclohexa-2,4-dienones
  作者：Julien Gagnepain、Raphaël Méreau、Delphine Dejugnac、Jean-Michel Léger、Frédéric Castet、Denis Deffieux、Laurent Pouységu、Stéphane Quideau

  DOI：10.1016/j.tet.2007.03.035

  日期：2007.7

  The [4+2] cyclodimerization of cyclohexa-2,4-dienone derivatives of the orthoquinone monoketal and orthoquinol types has been the topic of numerous investigations over the last 50 years in the aim of rationalizing the extraordinary level of regio-, site-, and stereoselectivities observed in these processes. In particular, the double diastereo-pi-facial differentiation expressed in cyclodimerizations of chiral orthoquinols (i.e., 6-alkyl-6-hydroxycyclohexa-2,4-dienones) is an important aspect of these transformations, for they relate to the construction of several natural products. The experimental and theoretical results that are described in this article offer a comprehensive understanding of the factors controlling these site- specific regio- and diastereoselectivities. Our interpretation of these results relies on a combination of Wood-ward-Hoffmann and Salem-Houk secondary orbital interactions and Cieplak-type hyperconjugative effects in bispericyclic C-2-symmetric transition states. (c) 2007 Elsevier Ltd. All rights reserved.