3-(2-bromopropionyl)-4,4-dibuthyl-5,5-pentamethylene-2-oxazolidone | 114341-93-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂螺癸烷衍生物
• 英文名称: 3-(2-bromopropionyl)-4,4-dibuthyl-5,5-pentamethylene-2-oxazolidone
• 英文别名: 3-(2-Bromopropionyl)-4,4-dibutyl-5,5-pentamethylene-2-oxazolidone；3-(2-bromopropionyl)4,4-dibutyl-5,5-pentamethylene-2-oxazolidone；3-(2'-bromopropionyl)-4,4-dibutyl-5,5-pentamethyleneoxazolidin-2-one；3-(2-Bromopropanoyl)-4,4-dibutyl-1-oxa-3-azaspiro[4.5]decan-2-one
• CAS: 114341-93-4
• 化学式: C₁₉H₃₂BrNO₃
• 分子量: 402.372
• InChiKey: TYIBHSWPCOIMMF-UHFFFAOYSA-N

物化性质

• 沸点：
  478.4±28.0 °C(predicted)
• 密度：
  1.23±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  3-(2-bromopropionyl)-4,4-dibuthyl-5,5-pentamethylene-2-oxazolidone 在 锌 作用下， 以 四氢呋喃 为溶剂， 生成 (3S,4R)-3-<(R)-1-hydroxyethyl>-4-<(R)-1-(4,4-dibutyl-5,5-pentamethylene-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone
  参考文献：
  名称：

  氯磺酰基异氰酸酯与4 H -1,3-二恶英衍生物的[2 + 2]-环加成反应新合成1β-甲基卡巴培南关键中间体

  摘要：

  通过特征在于氯磺酰基异氰酸酯与4 H -1,3-二恶英衍生物的[2 + 2]-环加成反应，可容易地从标题（Ba ）的（R）-3-羟基丁酸甲酯中获得，来探索标题化合物的高度立体选择性合成路线。-Villiger反应导致新的乙缩醛部分裂解，以及与空间拥挤的3-（2-溴丙酰基）-2-恶唑烷酮衍生物发生Reformatsky反应。

  DOI：

  10.1016/s0040-4039(01)93817-1
• 作为产物：
  描述：

  环己酮 在 正丁基锂 、 zinc(II) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 5.25h， 生成 3-(2-bromopropionyl)-4,4-dibuthyl-5,5-pentamethylene-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

• A highly stereoselective synthesis of the 1β-methylcarbapenem key intermediate from (R)-3-hydroxybutyric acid
  作者：Yuko Kobayashi、Yoshio Ito、Shiro Terashima

  DOI：10.1016/s0040-4020(01)80578-0

  日期：1992.1

  Baeyer-Villiger reaction accompanying novel cleavage of the acetal moiety. The Reformatsky reaction of 6 with sterically crowded 3-(2-bromopropionyl)-2-oxazolidone derivatives readily afforded the title key intermediate after sequential chemical manipulations.

  （3R，4R）-4-乙酰氧基-3-[（R）-1-（甲酰氧基）乙基] -2-氮杂环丁酮6可以通过[2 + 2 ]从（R）-3-羟基丁酸高立体选择性地制备氯磺酰基异氰酸酯与2H，4H-1,3-二恶英衍生物的]-环加成反应和伴随乙缩醛部分新裂解的Baeyer-Villiger反应。6与空间拥挤的3-（2-溴丙酰基）-2-恶唑烷酮衍生物的Reformatsky反应在连续的化学操作后很容易提供标题关键中间体。
• 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。
• Highly stereoselective reformatsky reactions of 3-(2-Bromopropionyl)-2-oxazolidone derivatives with various aldehydes
  作者：Yoshio Ito、Shiro Terashima

  DOI：10.1016/s0040-4020(01)87087-3

  日期：1991.1

  The Reformatsky reactions of 3-(2-bromopropionyl)-2-oxazolidone derivatives with various aldehydes were investigated to elucidate the effects of substituents in the 2-oxazolidone moieties on their diastereoselectivities. The highest 2,3-syn-diastereoselectivity (2,3-syn:2,3-anti = 98:2) could be realized at -78-degrees-C by employing sterically crowded 3-(2-bromopropionyl)-4,4-dibutyl-5,5-pentamethylene-2-oxazolidone. While high 2,3-syn-3,4-syn-selectivity (2,3-syn-3,4-syn:2,3-syn-3,4-anti = 94:6) was also accomplished by the reaction with dl-2-phenylpropanal, application of this reaction to enantioselective synthesis of 2,3-syn-aldols was found to be unrewarding. The observed diastereoselectivities could be accounted for by the chelating transition state models.
• A highly stereoselective synthesis of a key intermediate of 1β-methylcarbapenems employing the reformatsky reaction of 3-(2-bromopropionyl)-2-oxazolidone derivatives
  作者：Yoshio Ito、Shiro Terashima

  DOI：10.1016/s0040-4039(00)96930-2

  日期：——
• A highly stereoselective synthesis of aldols employing the Reformatsky reaction of 3-(2-bromopropionyl)-2-oxazolidone derivatives with various aldehydes
  作者：Yoshio Ito、Shiro Terashima

  DOI：10.1016/s0040-4039(00)96931-4

  日期：——