cis-4-[(2-bromo-1,1-dimethyl)ethyl]-3-methoxy-1-(2-methylallyl)azetidin-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: cis-4-[(2-bromo-1,1-dimethyl)ethyl]-3-methoxy-1-(2-methylallyl)azetidin-2-one
• 英文别名: cis-4-(2-bromo-1,1-dimethylethyl)-3-methoxy-1-(2-methylallyl)azetidin-2-one；(3S,4R)-4-(1-bromo-2-methylpropan-2-yl)-3-methoxy-1-(2-methylprop-2-enyl)azetidin-2-one
• 化学式: C₁₂H₂₀BrNO₂
• 分子量: 290.2
• InChiKey: FTNOSAQRXXPSAA-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-4-[(2-bromo-1,1-dimethyl)ethyl]-3-methoxy-1-(2-methylallyl)azetidin-2-one 、 甲醇 在 sodium methylate 作用下， 反应 4.0h， 以45%的产率得到Z-methyl 4,4-dimethyl-2-methoxy-5-(2-methylallylamino)pent-2-enoate
  参考文献：
  名称：

  Rearrangement of 4-(1-Haloalkyl)- and 4-(2-Haloalkyl)-2-azetidinones into Methyl ω-Alkylaminopentenoates via Transient Aziridines and Azetidines

  摘要：

  The synthesis of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones was investigated with use of the Staudinger reaction between in situ generated ketenes and alpha-haloimines or beta-haloimines. This new class of functionalized 2-azetidinones was further evaluated for its potential use as intermediates in the synthesis of highly functionalized compounds. The reaction of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones with sodium methoxide in methanol yielded ring-opened products, i.e., methyl 2-alkoxy-4-(alkylamino)pentenoate and methyl 5-(alkylamino)pentenoate, respectively. Further attention was paid in detail to the reaction mechanism involved in this peculiar transformation. It was proven that these reactions proceeded via intermediate aziridines or azetidines.

  DOI：

  10.1021/jo040161b
• 作为产物：
  描述：

  3-溴-2,2-二甲基丙醛 在 magnesium sulfate 、 三乙胺 作用下， 以 苯 为溶剂， 反应 0.5h， 生成 cis-4-[(2-bromo-1,1-dimethyl)ethyl]-3-methoxy-1-(2-methylallyl)azetidin-2-one
  参考文献：
  名称：

  Rearrangement of 4-(1-Haloalkyl)- and 4-(2-Haloalkyl)-2-azetidinones into Methyl ω-Alkylaminopentenoates via Transient Aziridines and Azetidines

  摘要：

  The synthesis of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones was investigated with use of the Staudinger reaction between in situ generated ketenes and alpha-haloimines or beta-haloimines. This new class of functionalized 2-azetidinones was further evaluated for its potential use as intermediates in the synthesis of highly functionalized compounds. The reaction of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones with sodium methoxide in methanol yielded ring-opened products, i.e., methyl 2-alkoxy-4-(alkylamino)pentenoate and methyl 5-(alkylamino)pentenoate, respectively. Further attention was paid in detail to the reaction mechanism involved in this peculiar transformation. It was proven that these reactions proceeded via intermediate aziridines or azetidines.

  DOI：

  10.1021/jo040161b

文献信息

• Novel Diastereoselective Synthesis of Bicyclic β-Lactams through Radical Cyclization and Their Reduction toward 2-(1-Alkoxy-2-hydroxyethyl)piperidines and 2-(1-Alkoxy-2-hydroxyethyl)azepanes
  作者：Erika Leemans、Matthias D'hooghe、Yves Dejaegher、Karl W. Törnroos、Norbert De Kimpe

  DOI：10.1021/jo702263p

  日期：2008.2.1

  1-Allyl- and 1-(3-phenylallyl)-substituted 4-(2-bromo-1,1-dimethylethyl)azetidin-2-ones were transformed into 3-substituted 7-alkoxy-5,5-dimethyl-1-azabicyclo[4.2.0]octane-8-ones through radical cyclization by means of n-tributyltin hydride and AIBN in toluene with excellent diastereocontrol (≥99%). The radical cyclization of 4-(2-bromo-1,1-dimethylethyl)-1-(2-methylallyl)azetidin-2-ones afforded 8-alkoxy-3

  将1-烯丙基和1-（3-苯基烯丙基）取代的4-（2-溴-1,1-二甲基乙基）氮杂环丁烷-2-酮转化为3-取代的7-烷氧基-5,5-二甲基-1-氮杂三环[4.2.0]辛烷-8-通过氢化正丁基三丁基锡和AIBN在甲苯中进行自由基环化，具有出色的非对映异构控制性（≥99％）。4-（2-溴-1,1-二甲基乙基）-1-（2-甲基烯丙基）氮杂环丁烷-2-酮的自由基环化提供了8-烷氧基-3,6,6-三甲基-1-氮杂双环[5.2.0 ] nonan-9-非对映异构体过量（75-78％）。1-氮杂双环[4.2.0]辛烷-8-酮和1-氮杂双环[5.2.0]壬南-9-酮与氢化铝锂的还原开环生成了新型的2-（1-烷氧基-2-羟乙基）哌啶和-azepanes，它们是作为单一异构体分离出来的。