tert-butyl ((2S,3S)-3-(2-((2R,3R)-3-(3-methoxy-4,4-diphenylbutyl)-3-methyloxiran-2-yl)ethyl)-3-methoxyoxiran-2-yl)methyl carbonate | 945266-02-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl ((2S,3S)-3-(2-((2R,3R)-3-(3-methoxy-4,4-diphenylbutyl)-3-methyloxiran-2-yl)ethyl)-3-methoxyoxiran-2-yl)methyl carbonate
• CAS: 945266-02-4
• 化学式: C₃₁H₄₂O₆
• 分子量: 510.671
• InChiKey: UQRJXGVNQAIBSE-GIKUQBPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.66
• 重原子数：
  37.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  69.82
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  tert-butyl ((2S,3S)-3-(2-((2R,3R)-3-(3-methoxy-4,4-diphenylbutyl)-3-methyloxiran-2-yl)ethyl)-3-methoxyoxiran-2-yl)methyl carbonate 在 4 A molecular sieve 、 N-methylquinolinium hexafluorophosphate air 、 sodium acetate 、 sodium thiosulfate 作用下， 以 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 4.5h， 生成 (R)-4-((2S,5S)-tetrahydro-5-((R)-tetrahydro-5-methoxy-2-methylfuran-2-yl)-2-methylfuran-2-yl)-1,3-dioxolan-2-one 、 (4aS,5aS,9aR,11aR)-8-methoxy-5a,11a-dimethyldecahydro-1,3,5,9-tetraoxadibenzo[a,d]cycloheptan-2-one
  参考文献：
  名称：

  An Experimental and Computational Approach to Defining Structure/Reactivity Relationships for Intramolecular Addition Reactions to Bicyclic Epoxonium Ions

  摘要：

  In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.

  DOI：

  10.1021/ja0709674
• 作为产物：
  描述：

  tert-butyl(((2E,6E)-10-methoxy-3,7-dimethyl-11,11-diphenylundeca-2,6-dien-1-yl)oxy)dimethylsilane 在 titanium(IV) isopropylate 、 Shi's ketone N-甲基咪唑 、 叔丁基过氧化氢 、 oxone 、 L-(+)-diisopropyl tartrate 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 生成 tert-butyl ((2S,3S)-3-(2-((2R,3R)-3-(3-methoxy-4,4-diphenylbutyl)-3-methyloxiran-2-yl)ethyl)-3-methoxyoxiran-2-yl)methyl carbonate
  参考文献：
  名称：

  An Experimental and Computational Approach to Defining Structure/Reactivity Relationships for Intramolecular Addition Reactions to Bicyclic Epoxonium Ions

  摘要：

  In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.

  DOI：

  10.1021/ja0709674