(3R)-3-benzyl-1-bis(trimethylsilyl)methyl-3-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]azetidin-2-one | 254112-83-9

• 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: (3R)-3-benzyl-1-bis(trimethylsilyl)methyl-3-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]azetidin-2-one
• 英文别名: (4S)-3-[(3R)-3-benzyl-1-[bis(trimethylsilyl)methyl]-2-oxoazetidin-3-yl]-4-phenyl-1,3-oxazolidin-2-one
• CAS: 254112-83-9
• 化学式: C₂₆H₃₆N₂O₃Si₂
• 分子量: 480.754
• InChiKey: SWPDGSWVMTUTFJ-ATIYNZHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R)-3-benzyl-1-bis(trimethylsilyl)methyl-3-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]azetidin-2-one 在 palladium on activated charcoal ammonium cerium(IV) nitrate 、 氨 、 氢气 、 lithium 、 碳酸氢钠 、 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 生成 (3R)-3-benzyl-3-tert-butoxycarbonylamino-1-carboxymethyl-azetidin-2-one
  参考文献：
  名称：

  α-Alkyl-α-Amino-β-Lactam Peptides: Design, Synthesis, and Conformational Features

  摘要：

  Remarkable asymmetric induction is achieved in the alkylation of the lithium enolate of the beta-lactam 1. This allows the first time access to a new family of peptidomimetics 2 with predictable conformational constraints.

  DOI：

  10.1002/(sici)1521-3773(19991018)38:20<3056::aid-anie3056>3.0.co;2-j
• 作为产物：
  描述：

  溴甲苯 、 (3S)-1-[bis(trimethylsilyl)methyl]-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以90%的产率得到(3R)-3-benzyl-1-bis(trimethylsilyl)methyl-3-[(4S)-2-oxo-4-phenyloxazolidin-3-yl]azetidin-2-one
  参考文献：
  名称：

  On the Question of the Diastereoselective Alkylation of 4-Unsubstituted 3-Amino β-Lactams. A Concise Synthesis of α-Branched α-Amino β-Lactams and their Coupling with α-Amino Acid Esters

  摘要：

  The reaction of [(4S)-2-oxo-4-phenyloxazolidin-3-yl]acetic acid chloride with N-methylidene-bis-[(trimethylsilyl)methyl] amine and triethylamine in refluxing chloroform leads to a 4-unsubstituted beta-lactam able to undergo highly asymmetric alkylations at the alpha-position of the beta-lactam ring. The resulting adducts can be efficiently transformed into N-unsubstituted alpha-branched 3-amino beta-lactams as the cyclisized forms of alpha-branched beta-aminoalanines or transformed into their imide N-Boc derivatives, which are suitable substrates for non-proteinogenic peptide synthesis, by reaction with alpha-amino esters. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00406-3

文献信息

• Functionalization of <i>N</i>-[(Silyl)methyl]-β-lactam Carbanions with Carbon Electrophiles
  作者：Claudio Palomo、Jesus M. Aizpurua、Ana Benito、Lourdes Cuerdo、Raluca M. Fratila、José I. Miranda、Anthony Linden

  DOI：10.1021/jo060537g

  日期：2006.8.1

  Latent acidity of alpha-alkyl-alpha-amino-N-[(silyl) methyl]-beta-lactams enabled a concise entry to lithium nonenolate N-methyl-azetidinone carbanions lithiated alpha' to the beta-lactam nitrogen, owing to the stabilizing "alpha-effect" of one or two trimethylsilyl groups. (BuLi)-Bu-n/TMEDA and 'BuLi/TMEDA were the bases of choice for complete deprotonation of di- and monosilylated beta-lactams, respectively. Trapping of the resulting carbanions with alkyl halides provided the corresponding N-[(alpha'-silyl)-alkyl]-beta-lactams, while carbon dioxide and related electrophiles such as benzyl chloroformates or isocyanates, afforded the corresponding silicon-free N-carboxymethyl-, N-benzyloxycarbonylmethyl-, and N-amidomethyl-beta-lactams in a single synthetic step. Likely structures of these unprecedented lithiated N-[(silyl) methyl]-beta-lactams were studied by MO calculations (B3LYP/6-31G*), and the origin of their relative stability was briefly discussed.
• On the Question of the Diastereoselective Alkylation of 4-Unsubstituted 3-Amino β-Lactams. A Concise Synthesis of α-Branched α-Amino β-Lactams and their Coupling with α-Amino Acid Esters
  作者：Claudio Palomo、Jesus M. Aizpurua、Regina Galarza、Ana Benito、Uttam K. Khamrai、Unni Eikeseth、Anthony Linden

  DOI：10.1016/s0040-4020(00)00406-3

  日期：2000.7

  The reaction of [(4S)-2-oxo-4-phenyloxazolidin-3-yl]acetic acid chloride with N-methylidene-bis-[(trimethylsilyl)methyl] amine and triethylamine in refluxing chloroform leads to a 4-unsubstituted beta-lactam able to undergo highly asymmetric alkylations at the alpha-position of the beta-lactam ring. The resulting adducts can be efficiently transformed into N-unsubstituted alpha-branched 3-amino beta-lactams as the cyclisized forms of alpha-branched beta-aminoalanines or transformed into their imide N-Boc derivatives, which are suitable substrates for non-proteinogenic peptide synthesis, by reaction with alpha-amino esters. (C) 2000 Elsevier Science Ltd. All rights reserved.
• α-Alkyl-α-Amino-β-Lactam Peptides: Design, Synthesis, and Conformational Features
  作者：Claudio Palomo、Jesus M. Aizpurua、Ana Benito、Regina Galarza、Uttam K. Khamrai、Jordi Vazquez、Beatriz de Pascual-Teresa、Pedro M. Nieto、Anthony Linden

  DOI：10.1002/(sici)1521-3773(19991018)38:20<3056::aid-anie3056>3.0.co;2-j

  日期：1999.10.18

  Remarkable asymmetric induction is achieved in the alkylation of the lithium enolate of the beta-lactam 1. This allows the first time access to a new family of peptidomimetics 2 with predictable conformational constraints.