1-((1aS,7bS)-7-Methoxy-2,2-dimethyl-1a,7b-dihydro-2H-1,3-dioxa-cyclopropa[a]naphthalen-6-yl)-ethanone | 209916-14-3

• 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: 1-((1aS,7bS)-7-Methoxy-2,2-dimethyl-1a,7b-dihydro-2H-1,3-dioxa-cyclopropa[a]naphthalen-6-yl)-ethanone
• 英文别名: 1-[(1aS,7bS)-7-methoxy-2,2-dimethyl-1a,7b-dihydrooxireno[2,3-c]chromen-6-yl]ethanone
• CAS: 209916-14-3
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: RVZDRSMCNHUBSH-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  48.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-(5-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethanone 在 Mn(III)salen <(S,S)-4> sodium hypochlorite 作用下， 以 二氯甲烷 为溶剂， 生成 1-((1aS,7bS)-7-Methoxy-2,2-dimethyl-1a,7b-dihydro-2H-1,3-dioxa-cyclopropa[a]naphthalen-6-yl)-ethanone
  参考文献：
  名称：

  Enantiomerically Pure Epoxychromans via Asymmetric Catalysis

  摘要：

  A practical and highly effective process for the asymmetric epoxidation of several 2,2-dimethylchromene derivatives is reported. Catalysis by Mn(salen) complex 4 in all cases affords epoxychromans with > 90% ee, and this method has been applied to the synthesis of two recently developed antihypertensive agents in enantiomerically pure form.

  DOI：

  10.1016/s0040-4039(00)93426-9

文献信息

• The first asymmetric epoxidation using a combination of achiral (salen)manganese(III) complex and chiral amine
  作者：Takashi Hashihayata、Yoshio Ito、Tsutomu Katsuki

  DOI：10.1016/s0040-4020(97)00633-9

  日期：1997.7

  system for asymmetric epoxidation was developed by using an achiral (salen)manganese(III) complex with chiral amine. Commercially available (-)-sparteine showed the highest asymmetric induction over the other chiral amines examined and addition of water to the reaction medium improved the induction up to 73% ee in the epoxidation of chromene derivative. Application of the system to the asymmetric oxidation

  通过使用非手性（salen）锰（III）与手性胺的配合物，开发了一种新的不对称环氧化催化剂体系。市售的（-）-天冬氨酸在所研究的其他手性胺上显示出最高的不对称诱导，向反应介质中加水可提高色烯衍生物的环氧化反应的诱导率，最高可达73％ee。还检查了该系统在甲基苯硫醚不对称氧化为其亚砜中的应用（至多25％ee）。这些结果支持了我们的建议，即Salen配体的非平面和手性结构在通过（salen）锰（III）络合物选择烯烃的对映体中起重要作用。
• What is the origin of highly asymmetric induction by a chiral (salen)manganese(III) complex? Design of a conformationally fixed complex and its application to asymmetric epoxidation of 2, 2-dimethylchromenes
  作者：Yoshio N. Ito、Tsutomu Katsuki

  DOI：10.1016/s0040-4039(98)00763-1

  日期：1998.6

  The optically active (salen)manganese(III) complex 1 having a carboxylate group on the ethylenediamine moiety was found to be an efficient catalyst for the asymmetric epoxidation of several 2,2-dimethylchromene derivatives (up to 99% ee). A high level of turn-over number (up to 9, 200) was also achieved in this epoxidation. The pseudo-axially oriented carboxylate in 1 was postulated to coordinate to the manganese ion and to fix the conformation of the salen ligand in the form enantiomeric to that of normal chiral (salen)manganese(III) complexes. This was supported by the absolute configurations of the produced epoxides. (C) 1998 Elsevier Science Ltd. All rights reserved.