(3S,4R)-3-<(R)-1-(t-Butyldimethylsilyloxy)ethyl>-4-<(S)-1-(4,4-dibutyl-5,5-pentamethylene-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone | 114418-66-5

• 英文名称: (3S,4R)-3-<(R)-1-(t-Butyldimethylsilyloxy)ethyl>-4-<(S)-1-(4,4-dibutyl-5,5-pentamethylene-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone
• 英文别名: (3S,4R)-3-[(R)-1-(t-Butyldimethylsilyloxy)ethyl]-4-[(S)-1-(4,4-dibutyl-5,5-pentamethylene-2-oxazolidone-3-carbonyl)ethyl]-2-azetidinone；4,4-dibutyl-3-[(2S)-2-[(2R,3S)-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanoyl]-1-oxa-3-azaspiro[4.5]decan-2-one
• CAS: 114418-66-5
• 化学式: C₃₀H₅₄N₂O₅Si
• 分子量: 550.855
• InChiKey: RPDLSKCIHCVXKL-OLKYXYMISA-N

物化性质

• 沸点：
  639.2±20.0 °C(predicted)
• 密度：
  1.06±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.95
• 重原子数：
  38.0
• 可旋转键数：
  11.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  84.94
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  (1S,3R,5R,6R)-8-aza-3-(benzyloxymethyl)-5-methyl-2,4-dioxa-bicyclo<4.2.0>octan-7-one 在 palladium dihydroxide 咪唑 、 氢气 、 calcium carbonate 、 锌 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 25.0~80.0 ℃ 、101.33 kPa 条件下， 反应 6.03h， 生成 (3S,4R)-3-<(R)-1-(t-Butyldimethylsilyloxy)ethyl>-4-<(S)-1-(4,4-dibutyl-5,5-pentamethylene-2-oxazolidone-3-carbonyl)ethyl>-2-azetidinone
  参考文献：
  名称：

  （R）-3-羟基丁酸的1β-甲基卡巴培南关键中间体的高度立体选择性合成

  摘要：

  （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。

  DOI：

  10.1016/s0040-4020(01)80578-0

文献信息

• A novel synthesis of the 1β-methylcarbapenem key intermediate employing the [2+2]-cycloaddition reaction of chlorosulfonyl isocyanate with a 4H-1,3-dioxin derivative
  作者：Yoshio Ito、Yuko Kobayashi、Shiro Terashima

  DOI：10.1016/s0040-4039(01)93817-1

  日期：1989.1

  synthetic route to the title compound was explored by featuring the [2+2]-cycloaddition reaction of chlorosulfonyl isocyanate with the 4H-1,3-dioxin derivative readily obtainable from methyl (R)-3-hydroxybutyrate, the Baeyer-Villiger reaction resulting in novel cleavage of the acetal moiety, and the Reformatsky reaction with sterically crowded 3-(2-bromopropionyl)-2-oxazolidone derivatives.

  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。
• 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.
• 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：——
• ITO, YOSHIO;TERASHIMA, SHIRO, TETRAHEDRON LETT., 28,(1987) N 52, 6625-6628
  作者：ITO, YOSHIO、TERASHIMA, SHIRO

  DOI：——

  日期：——