3-(2-Bromopropionyl)-4,4,5,5-tetramethyl-2-oxazolidone | 134225-24-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-(2-Bromopropionyl)-4,4,5,5-tetramethyl-2-oxazolidone
• 英文别名: 3-(2'-bromopropionyl)-4,4,5,5-tetramethyloxazolidin-2-one；3-(2-bromopropanoyl)-4,4,5,5-tetramethyl-1,3-oxazolidin-2-one
• CAS: 134225-24-4
• 化学式: C₁₀H₁₆BrNO₃
• 分子量: 278.146
• InChiKey: PMFSTJUHRZLRKI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-乙酰氧基氮杂环丁酮 、 3-(2-Bromopropionyl)-4,4,5,5-tetramethyl-2-oxazolidone 在 锌 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 (3S,4R)-3-<(R)-1-(t-Butyldimethylsilyloxy)ethyl>-4-<(R)-1-(4,4,5,5-tetramethyl-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone 、 (3S,4R)-3-<(R)-1-(t-Butyldimethylsilyloxy)ethyl>-4-<(S)-1-(4,4,5,5-tetramethyl-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone
  参考文献：
  名称：

  Highly stereocontrolled synthesis of the 1β-methylcarbapenem key intermediate by the reformatsky reaction of 3-(2-bromopropionyl)-2-oxazolidone derivatives with a 4-acetoxy-2-azetidinone

  摘要：

  The key synthetic intermediate (4) of 1-beta-methylcarbapenems (1 approximately 3) was efficiently synthesized by employing highly stereocontrolled Reformatsky reaction (C4-alkylation) of 3-(2-bromopropionyl)-2-oxazolidone derivatives (6) with (3R,4R)-4-acetoxy-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-2-azetidinone (5) in the presence of zinc dust followed by removal of 2-oxazolidone moieties. The best diastereoselectivity (beta:alpha = 95.5) could be realized by uses of sterically crowded achiral 2-oxazolidone derivatives such as 4,4-dimethyl-, 4,4,5,5-tetramethyl, and 4,4-dibutyl-5,5-pentamethylene-2-oxazolidone and higher reaction temperatures (refluxing tetrahydrofran). The remarkable diastereoselectivities observed for the Reformatsky reactions could be explained by means of the weakly chelating transition state models.

  DOI：

  10.1016/s0040-4020(01)87086-1
• 作为产物：
  描述：

  2-Amino-1,1,2-trimethyl-1-propanol 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 3-(2-Bromopropionyl)-4,4,5,5-tetramethyl-2-oxazolidone
  参考文献：
  名称：

  Highly stereocontrolled synthesis of the 1β-methylcarbapenem key intermediate by the reformatsky reaction of 3-(2-bromopropionyl)-2-oxazolidone derivatives with a 4-acetoxy-2-azetidinone

  摘要：

  The key synthetic intermediate (4) of 1-beta-methylcarbapenems (1 approximately 3) was efficiently synthesized by employing highly stereocontrolled Reformatsky reaction (C4-alkylation) of 3-(2-bromopropionyl)-2-oxazolidone derivatives (6) with (3R,4R)-4-acetoxy-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-2-azetidinone (5) in the presence of zinc dust followed by removal of 2-oxazolidone moieties. The best diastereoselectivity (beta:alpha = 95.5) could be realized by uses of sterically crowded achiral 2-oxazolidone derivatives such as 4,4-dimethyl-, 4,4,5,5-tetramethyl, and 4,4-dibutyl-5,5-pentamethylene-2-oxazolidone and higher reaction temperatures (refluxing tetrahydrofran). The remarkable diastereoselectivities observed for the Reformatsky reactions could be explained by means of the weakly chelating transition state models.

  DOI：

  10.1016/s0040-4020(01)87086-1

文献信息

• Heterocyclic compounds and their production
  申请人：Sumitomo Pharmaceuticals Company, Limited

  公开号：US05231179A1

  公开（公告）日：1993-07-27

  A compound of the formula: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each a hydrogen atom, a lower alkyl group, an ar(lower)alkyl group or an aryl group, or R.sub.1 and R.sub.2 may be combined together to form a lower alkylene group and/or R.sub.3 and R.sub.4 are combined together to form a lower alkylene group, or R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be combined together to form an o-phenylene group, X is a halogen atom and Y is an oxygen atom or a nitrogen atom substituted with lower alkyl or aryl, which is useful as an intermediate in the synthesis of 1.beta.-methylcarbapenem compounds valuable as antibiotics.

  其中R.sub.1、R.sub.2、R.sub.3和R.sub.4分别是氢原子、较低的烷基基团、取代芳基烷基基团或芳基，或者R.sub.1和R.sub.2可以结合形成较低的烷基烯基基团和/或R.sub.3和R.sub.4结合形成较低的烷基烯基基团，或者R.sub.1、R.sub.2、R.sub.3和R.sub.4可以结合形成o-苯基烯基基团，X是卤素原子，Y是氧原子或取代较低烷基或芳基的氮原子，这在1-β-甲基卡巴比那酮类抗生素的合成中作为中间体是有用的。
• US5231179A
  申请人：——

  公开号：US5231179A

  公开（公告）日：1993-07-27
• Highly stereocontrolled synthesis of the 1β-methylcarbapenem key intermediate by the reformatsky reaction of 3-(2-bromopropionyl)-2-oxazolidone derivatives with a 4-acetoxy-2-azetidinone
  作者：Yoshio Ito、Akira Sasaki、Kastumi Tamoto、Makoto Sunagawa、Shiro Terashima

  DOI：10.1016/s0040-4020(01)87086-1

  日期：1991.1

  The key synthetic intermediate (4) of 1-beta-methylcarbapenems (1 approximately 3) was efficiently synthesized by employing highly stereocontrolled Reformatsky reaction (C4-alkylation) of 3-(2-bromopropionyl)-2-oxazolidone derivatives (6) with (3R,4R)-4-acetoxy-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-2-azetidinone (5) in the presence of zinc dust followed by removal of 2-oxazolidone moieties. The best diastereoselectivity (beta:alpha = 95.5) could be realized by uses of sterically crowded achiral 2-oxazolidone derivatives such as 4,4-dimethyl-, 4,4,5,5-tetramethyl, and 4,4-dibutyl-5,5-pentamethylene-2-oxazolidone and higher reaction temperatures (refluxing tetrahydrofran). The remarkable diastereoselectivities observed for the Reformatsky reactions could be explained by means of the weakly chelating transition state models.