(3S,4R)-3-benzyl-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-oxazolidin-3-yl]-1-(trimethylsilylmethyl)-azetidin-2-one | 813440-50-5

• 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: (3S,4R)-3-benzyl-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-oxazolidin-3-yl]-1-(trimethylsilylmethyl)-azetidin-2-one
• 英文别名: (4S)-3-[(2R,3S)-3-benzyl-2-(2-methylpropyl)-4-oxo-1-(trimethylsilylmethyl)azetidin-3-yl]-4-phenyl-1,3-oxazolidin-2-one
• CAS: 813440-50-5
• 化学式: C₂₇H₃₆N₂O₃Si
• 分子量: 464.68
• InChiKey: FTPBCWKDGURNBH-OASJLCFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  (3S,4R)-3-benzyl-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-oxazolidin-3-yl]-1-(trimethylsilylmethyl)-azetidin-2-one 、 溴甲苯 在 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以50%的产率得到(3S)-1,3-dibenzyl-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one
  参考文献：
  名称：

  Functionalization of N-[(Silyl)methyl]-β-lactam Carbanions with Carbon Electrophiles

  摘要：

  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.

  DOI：

  10.1021/jo060537g
• 作为产物：
  描述：

  (3S,4R)-1-[bis(trimethylsilyl)methyl]-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-oxazolidin-3-yl]-azetidin-2-one 在 cesium fluoride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 2.17h， 生成 (3S,4R)-3-benzyl-4-isobutyl-3-[(4S)-4-phenyl-2-oxo-oxazolidin-3-yl]-1-(trimethylsilylmethyl)-azetidin-2-one
  参考文献：
  名称：

  Synthesis of Type II β-Turn Surrogate Dipeptides Based on syn-α-Amino-α,β-dialkyl-β-lactams

  摘要：

  The achiral bis(trimethylsilyl)methyl group acts as an efficient stereochemical determinant of the alpha-alkylation reaction in beta-branched alpha-phenyloxazolidinyl- or alpha-diphenyloxazolidinyl-beta-lactams and provides the first stereocontrolled access to syn-alpha-amino-alpha,beta-dialkyl(aryl)-beta-lactams. These products are readily transformed into type II beta-turn mimetic surrogates 2B.

  DOI：

  10.1021/ol048348c