(1aR-cis)-1a,7b-dihydro-2,2-dimethyl-2H-oxireno[c][1]benzopyran-6-carbonitrile

• 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: (1aR-cis)-1a,7b-dihydro-2,2-dimethyl-2H-oxireno[c][1]benzopyran-6-carbonitrile
• 英文别名: (1aR,7bR)-2,2-dimethyl-2,7b-dihydro-1aH-oxireno[2,3-c]chromene-6-carbonitrile；(3R,4R)-(+)-6-cyano-3,4-epoxy-2,2-dimethylchromane；(3R,4R)-3,4-Epoxy-6-cyano-2,2-dimethylchroman；(3R,4R)-2,2-dimethyl-6-cyanochromene oxide；(+)-(3R,4R)-6-cyano-3,4-epoxy-2,2-dimethylchromene；(1aR,7bR)-2,2-dimethyl-1a,7b-dihydrooxireno[2,3-c]chromene-6-carbonitrile
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: HCYIWPLDKSWKGY-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  45.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1aR-cis)-1a,7b-dihydro-2,2-dimethyl-2H-oxireno[c][1]benzopyran-6-carbonitrile 以 四氢呋喃 、 ammonium hydroxide 为溶剂， 生成 (3R-trans)-4-amino-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile
  参考文献：
  名称：

  4-arylamino-benzopyran and related compounds

  摘要：

  具有以下化学式##STR1##及其药用盐的化合物，其中X是烷基，Y是单键，--CH.sub.2 --，--C(O)--，--O--，--S--或--N(R.sup.8)--，其中R.sup.8是氢，烷基，卤代烷基，芳基，芳基烷基，环烷基或(环烷基)烷基，R.sup.1至R.sup.7如本文所定义。这些化合物具有钾通道激活活性，因此例如作为心血管药物是有用的。

  公开号：

  US05837702A1
• 作为产物：
  描述：

  2-乙酰基-4-氰基苯酚 在 四氢吡咯 、 sodium hypochlorite 、 sodium tetrahydroborate 、 disodium hydrogenphosphate 、 R,R-Jacobsen's catalyst 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 31.0h， 生成 (1aR-cis)-1a,7b-dihydro-2,2-dimethyl-2H-oxireno[c][1]benzopyran-6-carbonitrile
  参考文献：
  名称：

  Synthesis and Activity of Novel and Selective I_Ks-Channel Blockers

  摘要：

  Since the discovery of the I-Ks-potassium channel as the slowly activating component of the delayed rectifier current (I-k) in cardiac tissue, the search for blockers of this current has been intense. During the screening of K-ATP-channel openers of the chromanol type we found that chromanol 293B was able to block I-Ks. Chromanol 293B is a sulfonamide analogue of the K-ATP-channel openers but had no activity on this target. Experiments were initiated to improve the activity and properties based on this lead compound. As a screening model we used Xenopus oocytes injected with human minK (KCNE1). Variations of the aromatic substituent and the sulfonamide group were prepared, and their activity was evaluated. We found that the greatest influence on activity was found in the aromatic substituents. The most active compounds were alkoxy substituted. We chose HMR1556 ((3R, 4S)-(+)-N-[-3-hydroxy-2,2-dimethyl-6-(4,4,4-trifluorobutoxy)chroman-4-yl]-N-methyl-ethanesulfonamide) 10a for development as an antiarrhythmic drug. The absolute configuration, resulting from an X-ray single-crystal structure analysis, was determined.

  DOI：

  10.1021/jm0109255

文献信息

• Stereoselective Epoxidation of Alkenes with Hydrogen Peroxide using a Bipyrrolidine‐Based Family of Manganese Complexes
  作者：Isaac Garcia‐Bosch、Laura Gómez、Alfonso Polo、Xavi Ribas、Miquel Costas

  DOI：10.1002/adsc.201100409

  日期：2012.1

  Novel manganese complexes containing N4‐tetradentate ligands derived from chiral bipyrrolidinediamines catalyze the stereoselective epoxidation of a wide array of alkenes using low catalyst loadings (0.1 mol%) and hydrogen peroxide (1.2 equiv.) as terminal oxidant. This family of catalysts affords good to excellent yields (80–100%) and moderate to good ees (40–73%) in short reaction times (30 min)

  含有衍生自手性联吡咯烷二胺的N 4-四齿配体的新型锰配合物，使用低催化剂负载量（0.1 mol％）和过氧化氢（1.2当量）作为末端氧化剂，催化多种烯烃的立体选择性环氧化。该系列催化剂可有效利用过氧化氢，在较短的反应时间（30分钟）内提供良好至极佳的收率（80–100％）和中等至良好的ee s（40–73％）。
• Unusual solvent-effect in stereochemistry of asymmetric epoxidation using a (salen)chromium(III) complex as a catalyst
  作者：Hirotoshi Imanishi、Tsutomu Katsuki

  DOI：10.1016/s0040-4039(96)02274-5

  日期：1997.1

  Epoxidation of conjugated olefins has been examined with (salen)chromium(III) complexes as catalysts. Although (salen)chromium(III) complexes were catalytically less active than the corresponding (salen)manganese(III) complexes, the reactions with the chromium complexes were found to exhibit interesting solvent-dependent stereochemistry.

  已经用（salen）铬（III）配合物作为催化剂检查了共轭烯烃的环氧化。尽管（salen）铬（III）配合物的催化活性低于相应的（salen）锰（III）配合物，但发现与铬配合物的反应表现出有趣的溶剂依赖性立体化学。
• Nonheme Manganese-Catalyzed Asymmetric Oxidation. A Lewis Acid Activation versus Oxygen Rebound Mechanism: Evidence for the “Third Oxidant”
  作者：Roman V. Ottenbacher、Konstantin P. Bryliakov、Evgenii P. Talsi

  DOI：10.1021/ic101297x

  日期：2010.9.20

  oxidation sideways. However, the oxomanganese(IV) species were found to perform the Lewis acid activation of the acyl and alkyl hydroperoxides or iodosylarenes to form the new type of oxidant [oxomanganese(IV) complex with a terminal oxidant], with the latter accounting for the predominant enantioselective epoxidation pathway in the nonheme manganese-catalyzed olefin epoxidations.

  研究了一系列手性非血红素氨基吡啶基锰（II）配合物[LMn II（OTf）2 ]的催化性能。发现上述络合物可以用不同的氧化剂（过氧羧酸，氢过氧化物烷基，碘代芳烃等）以高转化率和选择性（高达100％）和对映体过量（高达79％）有效地催化对映选择性烯烃氧化为相应的环氧化物。 。探讨了配体结构对催化性能的影响。环氧化的对映选择性被认为是强烈地依赖于氧化剂（performic，过，以及结构中号氯过酸;叔-丁基和枯基氢过氧化物；因此，有证据表明末端氧化剂分子被掺入了氧转移中间体的结构中。高价电子顺磁共振活性锰配合物[LMN IV = O] 2+和[LMN IV（μ-O）2的Mn III L] 3+在起始催化剂与氧化剂相互作用时检测到H 2 O 3。高价络合物不会环氧化苯乙烯，它们本身只能导致较小的烯烃侧向氧化。然而，发现氧锰（IV）物种对酰基和氢过氧化物或碘代芳烃进行路易斯酸活化，形成新型氧化剂[具
• Reverse asymmetric catalytic epoxidation of unfunctionalized alkenes
  作者：Andreas Scheurer、Paul Mosset、Martina Spiegel、Rolf W. Saalfrank

  DOI：10.1016/s0040-4020(98)01106-5

  日期：1999.1

  from tartaric-derived alicyclic C2 symmetric vicinal diamines were studied in the catalysis of the asymmetric epoxidation of unfunctionalized alkenes. Although the enantioselectivities obtained were not as high as for Jacobsen and Katsuki catalysts, the most striking result was the reversed asymmetric induction.

  研究了由酒石酸脂环族C 2对称邻位二胺制备的新的Salen Mn（III）配合物在未官能化烯烃的不对称环氧化反应中的催化作用。尽管所获得的对映选择性不如Jacobsen和Katsuki催化剂高，但最显着的结果是反向不对称诱导。
• Reusable chiral macrocyclic Mn(III) salen complexes for enantioselective epoxidation of nonfunctionalized alkenes
  作者：Rukhsana I. Kureshy、Tamal Roy、Noor-ul H. Khan、Sayed H.R. Abdi、Arghya Sadhukhan、Hari C. Bajaj

  DOI：10.1016/j.jcat.2011.10.011

  日期：2012.2

  A series of new chiral monomeric and dimeric macrocyclic Mn(III) salen complexes 1–4 with trigol linker were synthesized, characterized (by microanalysis, IR spectroscopy, UV–vis. spectroscopy, optical rotation, and mass spectrometry), and used as catalysts in the enantioselective epoxidation of styrene, cis β-methyl styrene, indene, and chromenes in the presence of several N-oxides as an axial base

  一系列新的手性单体和二聚体大环的Mn（III）萨伦络合物的1 - 4与trigol接头合成，其特征在于（由元素分析，红外光谱，UV-可见光谱，旋光度，和质谱法），和用作催化剂苯乙烯，顺式β-甲基苯乙烯，茚和色烯的对映选择性环氧化反应，在0°C下存在几种N-氧化物作为轴向碱，NaOCl作为氧化剂。通过使用手性二聚大环催化剂3（2.5 mol％），可以以优异的收率（> 99％）和对映选择性（ee在某些情况下高达98％）获得对映纯的环氧化物。复杂4展示了回收利用（在保留对映体选择性的情况下最多可循环研究六个循环）在苯乙烯的不对称环氧化中。配合物4的动力学研究以苯乙烯的环氧化为代表底物，显示出对催化剂和氧化剂的一级依赖性，但与底物的初始浓度无关。