trans-1-<(R)-(Methoxycarbonyl)(phenyl)methyl>-3-(S)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4(S)-phenyl-2-azetidinone | 151490-63-0

• 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: trans-1-<(R)-(Methoxycarbonyl)(phenyl)methyl>-3-(S)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4(S)-phenyl-2-azetidinone
• 英文别名: methyl (2R)-2-[(3S,4S)-2-oxo-4-phenyl-3-(2,2,5,5-tetramethyl-1,2,5-azadisilolidin-1-yl)azetidin-1-yl]-2-phenylacetate
• CAS: 151490-63-0
• 化学式: C₂₄H₃₂N₂O₃Si₂
• 分子量: 452.701
• InChiKey: VWAGYTSAXPBUBC-BDTNDASRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.58
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-1-<(R)-(Methoxycarbonyl)(phenyl)methyl>-3-(S)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4(S)-phenyl-2-azetidinone 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 trans-3(S)-Amino-1-<(R)-(methoxycarbonyl)(phenyl)methyl>-4-(S)-phenyl-2-azetidinone
  参考文献：
  名称：

  Asymmetric Synthesis of .beta.-Lactams via the Zinc-Mediated Glycine Ester Enolate-Imine Condensation Reaction Using .alpha.-Amino Esters as the Chiral Auxiliary

  摘要：

  Imine esters of glycine, (R)-phenylglycine, (R)-(1,4-cyclohexadienyl)glycine and (S)-valine have been employed in the ester enolate-imine condensation via double activation with ZnCl2. The reaction of the chlorozinc enolate (1b) of ethyl (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)acetate with (R)-methyl N-benzylidene-2-phenylglycinate (2a) afforded the trans-beta-lactam 3a in 79% yield with excellent asymmetric induction (de >97%). Other imine esters also afforded trans-beta-lactams diastereoselectively, albeit in lower conversions (37-70%). Methyl (S)-2-[N-[3-(trimethylsilyl)-2-propyn-1-ylidene]amino]-3-methylbutanoate (2e) afforded a mixture of four diastereoisomers (68% conversion). The products were isolated as 3-phthalimido beta-lactams 5b-e and as 3-[(methoxycarbonyl)amino]-beta-lactam 6b. The reactivity of the zinc enolates and the diastereoselectivity of the reactions are discussed in terms of the coordination of the imine esters to ZnCl2 (template effect) and the stability and aggregation equilibria of the zinc enolates.

  DOI：

  10.1021/jo00119a009
• 作为产物：
  描述：

  N-benzylidenephenylglycine methyl ester 、 (1-乙氧基羰基甲基)-2,2,5,5-四甲基-1-氮杂-2,5-二硅杂环戊烷 在 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 生成 trans-1-<(R)-(Methoxycarbonyl)(phenyl)methyl>-3-(S)-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4(S)-phenyl-2-azetidinone 、 trans-3(S)-Amino-1-<(R)-(methoxycarbonyl)(phenyl)methyl>-4-(S)-phenyl-2-azetidinone
  参考文献：
  名称：

  Asymmetric Synthesis of .beta.-Lactams via the Zinc-Mediated Glycine Ester Enolate-Imine Condensation Reaction Using .alpha.-Amino Esters as the Chiral Auxiliary

  摘要：

  Imine esters of glycine, (R)-phenylglycine, (R)-(1,4-cyclohexadienyl)glycine and (S)-valine have been employed in the ester enolate-imine condensation via double activation with ZnCl2. The reaction of the chlorozinc enolate (1b) of ethyl (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)acetate with (R)-methyl N-benzylidene-2-phenylglycinate (2a) afforded the trans-beta-lactam 3a in 79% yield with excellent asymmetric induction (de >97%). Other imine esters also afforded trans-beta-lactams diastereoselectively, albeit in lower conversions (37-70%). Methyl (S)-2-[N-[3-(trimethylsilyl)-2-propyn-1-ylidene]amino]-3-methylbutanoate (2e) afforded a mixture of four diastereoisomers (68% conversion). The products were isolated as 3-phthalimido beta-lactams 5b-e and as 3-[(methoxycarbonyl)amino]-beta-lactam 6b. The reactivity of the zinc enolates and the diastereoselectivity of the reactions are discussed in terms of the coordination of the imine esters to ZnCl2 (template effect) and the stability and aggregation equilibria of the zinc enolates.

  DOI：

  10.1021/jo00119a009

文献信息

• (R)-2-phenylglycine as a chiral auxiliary in the asymmetric synthesis of 2-azetidinones
  作者：Hendrik L. van Maanen、Johann T.B.H. Jastrzebski、Jan Verweij、Antonius P.G. Kieboom、Anthony L. Spek、Gerard van Koten

  DOI：10.1016/s0957-4166(00)80336-5

  日期：1993.7

  The chlorozinc enolate of ethyl-[(2,2,5,5-tetramethyl-1-aza-2,5-disila)cyclopentyl]-acetate was reacted with the ZnCl2 complex of N-benzylidene-2-phenylglycine methyl ester in THF at −70 °C. After removal of the protecting silyl moiety (3S, 4S, αR)-1-(methoxycarbonyl)(phenyl)methyl-3-amino-4-phenyl-2-azetidinone was obtained in 73% yield with >97% d.e.. By treatment with aqueous ammonia complete epimerization

  使乙基[（（2,2,5,5-四甲基-1-氮杂-2,5-二硅基）环戊基]-乙酸乙酯的氯锌烯醇盐与N-亚苄基-2-苯基甘氨酸甲酯的ZnCl 2络合物反应， THF在-70°C下。除去保护性甲硅烷基部分（3S，4S，αR）-1-（甲氧基羰基）（苯基）甲基-3-氨基-4-苯基-2-氮杂环丁酮后，产率为73％，de＞ 97％。通过用氨水处理，完成了在α位的完全差向异构化。从THF中结晶出（3S，4S，αS）对映异构体，并通过X-射线晶体学确定绝对构型。
• Asymmetric Synthesis of .beta.-Lactams via the Zinc-Mediated Glycine Ester Enolate-Imine Condensation Reaction Using .alpha.-Amino Esters as the Chiral Auxiliary
  作者：Hendrik L. van Maanen、Henk Kleijn、Johann T. B. H. Jastrzebski、Jan Verweij、Antonius P. G. Kieboom、Gerard van Koten

  DOI：10.1021/jo00119a009

  日期：1995.7

  Imine esters of glycine, (R)-phenylglycine, (R)-(1,4-cyclohexadienyl)glycine and (S)-valine have been employed in the ester enolate-imine condensation via double activation with ZnCl2. The reaction of the chlorozinc enolate (1b) of ethyl (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)acetate with (R)-methyl N-benzylidene-2-phenylglycinate (2a) afforded the trans-beta-lactam 3a in 79% yield with excellent asymmetric induction (de >97%). Other imine esters also afforded trans-beta-lactams diastereoselectively, albeit in lower conversions (37-70%). Methyl (S)-2-[N-[3-(trimethylsilyl)-2-propyn-1-ylidene]amino]-3-methylbutanoate (2e) afforded a mixture of four diastereoisomers (68% conversion). The products were isolated as 3-phthalimido beta-lactams 5b-e and as 3-[(methoxycarbonyl)amino]-beta-lactam 6b. The reactivity of the zinc enolates and the diastereoselectivity of the reactions are discussed in terms of the coordination of the imine esters to ZnCl2 (template effect) and the stability and aggregation equilibria of the zinc enolates.