(5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride
• 英文别名: (5aR,10bS)-2-mesityl-5a,10b-dihydro-4H,6H-indeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazin-2-ium chloride；2-mesityl-6,10b-dihydro-4H,5aH-(5R)-oxa-3,10c-diaza-(2S)-azoniacyclopenta[c]fluorene chloride；Bode catalyst；Bode Catalyst 2；(1S,9R)-4-(2,4,6-trimethylphenyl)-8-oxa-4,5-diaza-2-azoniatetracyclo[7.7.0.02,6.011,16]hexadeca-2,5,11,13,15-pentaene;chloride
• 化学式: C₂₁H₂₂N₃O*Cl
• 分子量: 367.878
• InChiKey: GUECWMLEUCWYOS-WKOQGQMTSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.13
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride 在 重水 作用下， 以 氘代二甲亚砜 为溶剂， 反应 0.5h， 以84%的产率得到
  参考文献：
  名称：

  N-杂环卡宾/硫脲/叔胺多催化协同用磺酰亚胺对映体进行烯类的对映选择性磺化

  摘要：

  许多手轻而易举：在烯酮的有机催化不对称磺化中，N-杂环卡宾（NHC）催化剂对磺酰基亚胺的活化导致亚砜阴离子的释放，该亚砜阴离子经过亲核加成后成为烯酮。该过程的对映选择性是通过手性硫脲/胺助催化剂通过阴离子识别和氢键相互作用来控制的。Tol = p-甲苯基。

  DOI：

  10.1002/anie.201305023
• 作为产物：
  描述：

  (4AS,9AR)-4,4A,9,9A-四氢茚并[2,1-B][1,4]噁嗪-3(2H)-酮 在 盐酸 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 氯苯 为溶剂， 反应 26.5h， 生成 (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride
  参考文献：
  名称：

  Oxyanion Steering and CH−π Interactions as Key Elements in an N-Heterocyclic Carbene-Catalyzed [4 + 2] Cycloaddition

  摘要：

  The N-heterocyclic carbene catalyzed [4 + 2] cycloaddition has been shown to give gamma,delta-unsaturated delta-lactones in excellent enantio- and diastereoselectivity. However, preliminary computational studies of the geometry of the intermediate enolate rendered ambiguous both the origins of selectivity and the reaction pathway. Here, we show that a concerted, but highly asynchronous, Diels-Alder reaction occurs rather than the stepwise Michael-type or Claisen-type pathways. In addition, two crucial interactions are identified that enable high selectivity an oxyanion-steering mechanism and a CH-pi interaction. The calculations accurately predict the enantioselectivity of a number of N-heterocyclic carbene catalysts in the hetero-Diels-Alder reaction.

  DOI：

  10.1021/ja302761d
• 作为试剂：
  描述：

  氯乙醛 、 N,N'-3,5-cyclohexadiene-1,2-diylidenebis(benzamide) 在 (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride 、 sodium acetate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以31%的产率得到(2-oxo-2,3-dihydroquinoxaline-1,4-diyl)bis(phenylmethanone)
  参考文献：
  名称：

  Carbene-Catalyzed α-Carbon Amination of Chloroaldehydes for Enantioselective Access to Dihydroquinoxaline Derivatives

  摘要：

  An NHC-catalyzed alpha-carbon amination of chloroaldehydes was developed. Cyclohexadiene-1,2-diimines are used as amination reagents and four-atom synthons. Our reaction affords optically enriched dihydroquinoxalines that are core structures in natural products and synthetic bioactive molecules.

  DOI：

  10.1021/acs.orglett.9b01520

文献信息

• Enantioselective N-heterocyclic carbene catalyzed formal [3+2] cycloaddition using α-aroyloxyaldehydes and oxaziridines
  作者：Ryan W.F. Kerr、Mark D. Greenhalgh、Alexandra M.Z. Slawin、Polly L. Arnold、Andrew D. Smith

  DOI：10.1016/j.tetasy.2016.10.012

  日期：2017.1

  An enantioselective N-heterocyclic carbene catalysed formal [3+2] cycloaddition has been developed for the synthesis of oxazolindin-4-one products. The reaction of oxaziridines and alpha-aroyloxyaldehydes under N-heterocyclic carbene catalysis provides the formal cycloaddition products with excellent control of the diastereo- and enantioselectivity (12 examples, up to >95:5 dr, >99:1 er). A matched-mismatched effect between the enantiomer of the catalyst and oxaziridine was identified, and preliminary mechanistic studies have allowed the proposal of a model to explain these observations. (C) 2016 Published by Elsevier Ltd.
• Enantioselective Sulfonation of Enones with Sulfonyl Imines by Cooperative N-Heterocyclic-Carbene/Thiourea/Tertiary-Amine Multicatalysis
  作者：Zhichao Jin、Jianfeng Xu、Song Yang、Bao-An Song、Yonggui Robin Chi

  DOI：10.1002/anie.201305023

  日期：2013.11.18

  make light work: In an organocatalytic asymmetric sulfonation of enones, the activation of a sulfonyl imine by an N‐heterocyclic carbene (NHC) catalyst led to the release of a sulfinic anion, which underwent nucleophilic addition to the enone. The enantioselectivity of the process was controlled by a chiral thiourea/amine co‐catalyst through anion recognition and hydrogen‐bonding interactions. Tol=p‐tolyl

  许多手轻而易举：在烯酮的有机催化不对称磺化中，N-杂环卡宾（NHC）催化剂对磺酰基亚胺的活化导致亚砜阴离子的释放，该亚砜阴离子经过亲核加成后成为烯酮。该过程的对映选择性是通过手性硫脲/胺助催化剂通过阴离子识别和氢键相互作用来控制的。Tol = p-甲苯基。
• Oxyanion Steering and CH−π Interactions as Key Elements in an N-Heterocyclic Carbene-Catalyzed [4 + 2] Cycloaddition
  作者：Scott E. Allen、Jessada Mahatthananchai、Jeffrey W. Bode、Marisa C. Kozlowski

  DOI：10.1021/ja302761d

  日期：2012.7.25

  The N-heterocyclic carbene catalyzed [4 + 2] cycloaddition has been shown to give gamma,delta-unsaturated delta-lactones in excellent enantio- and diastereoselectivity. However, preliminary computational studies of the geometry of the intermediate enolate rendered ambiguous both the origins of selectivity and the reaction pathway. Here, we show that a concerted, but highly asynchronous, Diels-Alder reaction occurs rather than the stepwise Michael-type or Claisen-type pathways. In addition, two crucial interactions are identified that enable high selectivity an oxyanion-steering mechanism and a CH-pi interaction. The calculations accurately predict the enantioselectivity of a number of N-heterocyclic carbene catalysts in the hetero-Diels-Alder reaction.