2-((E)-2-Bromo-3-phenyl-allyl)-2-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-benzo[1,3]dioxin-2-ylmethyl)-malonic acid diethyl ester | 186038-44-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 2-((E)-2-Bromo-3-phenyl-allyl)-2-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-benzo[1,3]dioxin-2-ylmethyl)-malonic acid diethyl ester
• CAS: 186038-44-8
• 化学式: C₂₈H₃₉BrO₆
• 分子量: 551.518
• InChiKey: NHWCTGGHHISFIY-OTUUDDROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  35.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2-((E)-2-Bromo-3-phenyl-allyl)-2-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-benzo[1,3]dioxin-2-ylmethyl)-malonic acid diethyl ester 在 偶氮二异丁腈 、 三丁基氯化锡 、 sodium cyanoborohydride 作用下， 以 叔丁醇 为溶剂， 反应 5.0h， 以65%的产率得到
  参考文献：
  名称：

  Designed Chiral Acyl Radical Equivalents. Preparation and Cyclizations of Disymmetrically Substituted 1,3-Dioxabicyclo[4.4.0]decan-2-yl Radicals

  摘要：

  The diastereoselectivity of 5-exo-trigonal cyclizations of 2-(4 2-(4penten-1-yl)-1,3-dioxolan-2-yl and 2-(4penten-1-yl)-1,3-dioxan-2-yl radicals is investigated. When dioxolanes or dioxanes derived from C-2 symmetrically substituted diols are employed the diastereoselectivity is poor. In the dioxanyl series this is a consequence of the cyclization occurring through a twist-boat conformer. Disymmetrically substituted dioxanyl radicals, derived from the alcohols 21 and 41, are, however, constrained to chairlike conformations and accordingly give rise to highly diastereoselective cyclizations. Conditions are described for the hydrolysis of the resulting spiroacetals and for determination of the ee of the resulting 2-methylcyclopentanones.

  DOI：

  10.1021/jo961750n
• 作为产物：
  描述：

  Trans-p-Menthane-3,8-diol 、 2-bromo-4,4-bis(ethoxycarbonyl)-6,6-diethoxy-1-phenyl-1-hexene 在 camphor-10-sulfonic acid 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以92%的产率得到2-((E)-2-Bromo-3-phenyl-allyl)-2-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-benzo[1,3]dioxin-2-ylmethyl)-malonic acid diethyl ester
  参考文献：
  名称：

  Designed Chiral Acyl Radical Equivalents. Preparation and Cyclizations of Disymmetrically Substituted 1,3-Dioxabicyclo[4.4.0]decan-2-yl Radicals

  摘要：

  The diastereoselectivity of 5-exo-trigonal cyclizations of 2-(4 2-(4penten-1-yl)-1,3-dioxolan-2-yl and 2-(4penten-1-yl)-1,3-dioxan-2-yl radicals is investigated. When dioxolanes or dioxanes derived from C-2 symmetrically substituted diols are employed the diastereoselectivity is poor. In the dioxanyl series this is a consequence of the cyclization occurring through a twist-boat conformer. Disymmetrically substituted dioxanyl radicals, derived from the alcohols 21 and 41, are, however, constrained to chairlike conformations and accordingly give rise to highly diastereoselective cyclizations. Conditions are described for the hydrolysis of the resulting spiroacetals and for determination of the ee of the resulting 2-methylcyclopentanones.

  DOI：

  10.1021/jo961750n

文献信息

• Diastereoselective Cyclizations of 1,3-Dioxan-2-yl Radicals:  Chiral Acyl Radical Equivalents
  作者：Michèle P. Bertrand、David Crich、Robert Nouguier、Raghu Samy、Didier Stien

  DOI：10.1021/jo960705c

  日期：1996.1.1