3,4-epoxy-2,2-dimethylchroman | 87894-83-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 3,4-epoxy-2,2-dimethylchroman
• 英文别名: 2,2-dimethyl-1a,7b-dihydro-2H-oxireno[c]chromene；2,2-dimethyl-1a,7b-dihydrooxireno[2,3-c]chromene
• CAS: 87894-83-5
• 化学式: C₁₁H₁₂O₂
• mdl: MFCD12027201
• 分子量: 176.215
• InChiKey: AXWDPRJZZIUQPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.454
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,4-epoxy-2,2-dimethylchroman 在 吡啶 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 乙醇 为溶剂， 反应 2.0h， 生成 descyano-bimakalim
  参考文献：
  名称：

  6-Substituted Benzopyrans as Potassium Channel Activators:  Synthesis, Vasodilator Properties, and Multivariate Analysis

  摘要：

  During the last 10 years compounds have been discovered which can activate or block K-ATP channels. In particular, K channel activators (KCA)have been found to be smooth muscle relaxants with their main utility in hypertension and bronchodilation. In this paper we describe the synthesis of new KCA of the benzopyran type with a fixed 4-substituent and a systematic variation in the 6-position. The relaxant potency in rat aorta and trachea was used for biological characterization of the benzopyrans. In both biological test systems, they exhibit potency ranges of more than 3 log units. Structure-activity relationships are investigated by principal component analysis (PCA) and partial least-squares (PLS) analysis. Most striking outliers in an initial PLS analysis of the entire database were the unsubstituted 6-H compound 13 as well as 34 and 35. For the remaining set of 31 compounds, a S-component PLS model explains the variance in biological activity to 81% in the aortic and to 82% in the tracheal test system. 6-Substituents influence affinity by a direct (presumably dipolar) interaction with the receptor site. According to the 2D-plot of the partial PLS weights, a strong electronegativity as well as high values for the integy moment and for the heat of formation in water dominate the first component; low values for substituent size (as defined by globularity or surface) are in addition favorable for high potency. High lipophilicity and low minimum energies of interaction dominate the second component. Chemical descriptors for the biological potency of the test set in rat aorta and rat trachea are very similar according to the almost identical projection of the Y-variables onto the X-component space.

  DOI：

  10.1021/jm981047m
• 作为产物：
  描述：

  2,2,-二甲基-2H-苯并吡喃 在 2,6-二甲基吡啶 、 丙醛二乙基乙缩醛 、 bis(3-methyl-2,4-pentanedionato)cobalt(II) 、 4 A molecular sieve 、 氧气 作用下， 45.0 ℃ 、101.32 kPa 条件下， 反应 11.0h， 以77%的产率得到3,4-epoxy-2,2-dimethylchroman
  参考文献：
  名称：

  钴(II)配合物催化分子氧和醛缩醛联用制备烯烃制备酸敏环氧化物的新方法

  摘要：

  通过在常压下分子氧和醛缩醛的协同作用，将相应的烯烃氧化，并在钴催化下，成功地合成了酸敏感环氧化物，如色烯氧化物或γ,δ-不饱和醇的环氧化物（ II) 与 1,3-二酮配体配位的复合物。反应在温和且中性的条件下进行，并以良好的收率获得所需的环氧化物。在本反应条件下，既没有观察到过氧化也没有观察到形成的环氧化物分解。此外，各种甲硅烷基烯醇醚和甲硅烷基烯酮缩醛，酸敏感化合物，也分别顺利地单氧化成相应的 α-羟基酮和 α-羟基羧酸酯。

  DOI：

  10.1246/bcsj.67.2195

文献信息

• Controlled Exchange of Achiral Linkers with Chiral Linkers in Zr-Based UiO-68 Metal–Organic Framework
  作者：Chunxia Tan、Xing Han、Zijian Li、Yan Liu、Yong Cui

  DOI：10.1021/jacs.8b09606

  日期：2018.11.28

  linker MOFs are active and efficient catalysts for asymmetric cyanosilylation of aldehydes, ring-opening of epoxides, oxidative kinetic resolution of secondary alcohols, and aminolysis of stilbene oxide, and the mixed-M(salen) linker variants are active for sequential asymmetric alkene epoxidation/epoxide ring-opening reactions. The chiral MOF catalysts are highly enantioselective and completely heterogeneous

  开发用于广泛不对称反应的高度稳健的多相催化剂一直是一个令人感兴趣的主题，但它仍然是一个合成挑战。在这里，我们证明了具有潜在酸不稳定手性催化剂的高度稳定的金属有机骨架 (MOF) 可以通过合成后交换合成。通过一步或两步配体交换，一系列具有相同或不同金属中心的不对称金属盐催化剂结合到 Zr 基 UiO-68 MOF 中，形成单和混合 M(salen) 连接体晶体，其中不能通过直接溶剂热合成来完成。由此产生的 MOF 已通过各种技术进行表征，包括单晶 X 射线衍射、N2 吸附、CD 和 SEM/TEM-EDS 映射。单 M(salen) 接头 MOF 是醛的不对称氰基硅烷化、环氧化物的开环、仲醇的氧化动力学拆分和二苯乙烯氧化物的氨解的活性和有效催化剂，混合 M(salen) 接头变体是对连续的不对称烯烃环氧化/环氧化物开环反应具有活性。手性 MOF 催化剂具有高度的对映选择性、完全非均相和可回收
• Manganese catalysed asymmetric cis-dihydroxylation with H2O2
  作者：Johannes W. de Boer、Wesley R. Browne、Syuzanna R. Harutyunyan、Laura Bini、Theodora D. Tiemersma-Wegman、Paul L. Alsters、Ronald Hage、Ben L. Feringa

  DOI：10.1039/b808355j

  日期：——

  High turnover enantioselectivealkenecis-dihydroxylation is achieved with H2O2 catalysed by manganese based complexes containing chiral carboxylato ligands.

  高周转的对映选择性烯烃顺式二羟基化反应是通过含有手性羧酸盐配体的锰基配合物催化，使用 H2O2 实现的。
• Multivariate Metal–Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions
  作者：Qingchun Xia、Zijian Li、Chunxia Tan、Yan Liu、Wei Gong、Yong Cui

  DOI：10.1021/jacs.7b03113

  日期：2017.6.21

  The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural

  长期以来，人们对寻找具有多个活性位点的多功能多相催化剂进行广泛的不对称转化一直很感兴趣，但它仍然是一个艰巨的合成挑战。在这里，我们证明了多元金属有机框架 (MTV-MOF) 可用作设计具有多个协同活性位点的多相催化剂的绝佳平台。构建了包含多达三种不同手性金属盐催化剂的 2 倍互穿 MTV-MOF 的同构系列，并将其用作各种不对称顺序烯烃环氧化/环氧化物开环反应的高效且可回收的多相催化剂。框架的相互渗透使金属盐单元彼此相邻，允许协同激活，这导致在单个部分的总和上提高效率和对映选择性。在 MTV-MOF 中操纵分子催化剂可以控制活性和选择性的事实将有助于设计用于对映选择性过程的新型多功能材料。
• An effective procedure for the synthesis of acid-sensitive epoxides: Use of 1-methylimidazole as the additive on methyltrioxorhenium-catalyzed epoxidation of alkenes with hydrogen peroxide
  作者：Shigekazu Yamazaki

  DOI：10.1039/b926575a

  日期：——

  An effective method for suppression of ring opening and rearrangement of acid-sensitive epoxides during methyltrioxorhenium(MTO)-catalyzed epoxidation of alkenes with H2O2 by using 1-methylimidazole as a co-additive has been found. The combined use of 3-methylpyrazole and 1-methylimidazole as the additives has been found to be an effective procedure that affords excellent yields of acid-sensitive epoxides for MTO-catalyzed epoxidation.

  已发现一种有效的方法，通过使用1-甲基咪唑作为共添加剂，抑制在过氧化氢催化的烯烃环氧化反应中酸敏感环氧化物的开环和重排。这种将3-甲基吡唑和1-甲基咪唑联合用作添加剂的方法被证明是一种有效的程序，可以为MTO催化的环氧化反应提供优秀的酸敏感环氧化物产率。
• Epoxidation of Olefinic Compounds with Combined Use of Molecular Oxygen and Propionaldehyde Diethyl Acetal Catalyzed by Cobalt(II) Complex. Efficient Method for the Preparation of Acid-sensitive Epoxides
  作者：Kiyotaka Yorozu、Toshihiro Takai、Tohru Yamada、Teruaki Mukaiyama

  DOI：10.1246/cl.1993.1579

  日期：1993.9

  Synthesis of acid-sensitive epoxides such as epoxide of bishomoallyl alcohol or chromene oxide was achieved by the epoxidation of corresponding olefins with combined use of molecular oxygen and propionaldehyde diethyl acetal catalyzed by cobalt(II) complex. Various silyl enol ethers and silyl ketene acetals, acid-sensitive compounds, were also smoothly monooxygenated into the corresponding α-hydroxy

  通过在钴（II）配合物的催化下，通过分子氧和丙醛二乙缩醛的组合使用相应烯烃的环氧化反应来合成酸敏感的环氧化物，例如双单烯丙醇的环氧化物或氧化色烯。各种甲硅烷基烯醇醚和甲硅烷基乙烯酮缩醛，酸敏感化合物，也顺利地单氧化成相应的α-羟基羰基化合物。