(3S)-1-[bis(trimethylsilyl)methyl]-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one | 187161-86-0

• 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: (3S)-1-[bis(trimethylsilyl)methyl]-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one
• 英文别名: (3S)-1-bis(trimethylsilyl)methyl-3-[(4S)-2-oxo-4-phenylazolidin-3-yl]azetidin-2-one；(4S)-3-[(3S)-1-[bis(trimethylsilyl)methyl]-2-oxoazetidin-3-yl]-4-phenyl-1,3-oxazolidin-2-one
• CAS: 187161-86-0
• 化学式: C₁₉H₃₀N₂O₃Si₂
• 分子量: 390.63
• InChiKey: XHMRZFOLVGKRED-JKSUJKDBSA-N

物化性质

• 沸点：
  541.3±50.0 °C(Predicted)
• 密度：
  1.105±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 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)-1-[bis(trimethylsilyl)methyl]-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one 在 氨 、 lithium 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 (3R)-1-[bis(trimethylsilyl)-methyl]-3-tert-butoxycarbonylamino-3-isobutylazetidin-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：

  2-(4(S)-phenyloxazolidin-2-on-3-yl)acetyl chloride 在 potassium permanganate 、 sodium periodate 、 草酰氯 、 二甲基硫 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 、 臭氧 、 三乙胺 作用下， 以 二氯甲烷 、 氯仿 、 丙酮 、 甲苯 为溶剂， 反应 26.17h， 生成 (3S)-1-[bis(trimethylsilyl)methyl]-3-[(4S)-4-phenyl-2-oxo-1,3-oxazolidin-3-yl]azetidin-2-one
  参考文献：
  名称：

  A Contribution to the Asymmetric Synthesis of 3-Amino β-Lactams: The Diastereoselective [2+2] Cycloaddition Reaction of Chiral Aminoketene Equivalents with Enolizable Aldehyde-Derived Imines

  摘要：

  AbstractN‐[Bis(trimethylsilyl)methyl]imines 9 show unique chemical properties when compared with conventional imines. Their reaction with optically pure aminoketenes derived from dehydrochlorination of 14 and 15 affords the corresponding 3‐amino‐4‐alkyl‐β‐lactams 16 and 17 in good yields and high diastereoselectivities. The mild deprotection of bis(trimethylsilyl)methyl‐ and phenyloxazolidinone moieties with, respectively, cerium(IV) ammonium nitrate and lithium/ammonia or hydrogen/Pd(OH)2 allows the preparation of a variety of β‐lactam antibiotic building blocks.

  DOI：

  10.1002/chem.19970030909

文献信息

• Development of a New Family of Conformationally Restricted Peptides as Potent Nucleators of β-Turns. Design, Synthesis, Structure, and Biological Evaluation of a β-Lactam Peptide Analogue of Melanostatin
  作者：Claudio Palomo、Jesus M. Aizpurua、Ana Benito、José Ignacio Miranda、Raluca M. Fratila、Carlos Matute、Maria Domercq、Federico Gago、Sonsoles Martin-Santamaria、Anthony Linden

  DOI：10.1021/ja038180a

  日期：2003.12.1

  annealing techniques, showing a strong tendency to form stable type II or type II' beta-turns either in the solid state or in highly coordinating DMSO solutions. Tetrapeptide models containing syn- or anti-alpha,beta-dialkyl-alpha-amino-beta-lactam rings have also been synthesized and their conformations analyzed, revealing that alpha-alkyl substitution is essential for beta-turn stabilization. A beta-lactam

  新型对映体纯 (i)-(β-内酰胺)-(Gly)-(i+3) 肽模型，定义为存在中心 α-烷基-α-氨基-β-内酰胺环，放置为 (i+1 ) 残基，通过合适的 N-[双(三甲基甲硅烷基)甲基]-β-内酰胺的α-烷基化以完全立体控制的方式合成。这些 β-内酰胺假肽的结构特性已经通过 X 射线晶体学、分子动力学模拟和 NOESY 抑制 NMR 模拟退火技术进行了研究，显示出形成稳定的 II 型或 II 型'β-转角的强烈趋势。固态或高度协调的 DMSO 溶液。还合成了含有顺式或反式 α,β-二烷基-α-氨基-β-内酰胺环的四肽模型并分析了它们的构象，揭示α-烷基取代对于β-转角稳定是必不可少的。还制备了黑色素抑制素的 β-内酰胺类似物（PLG 酰胺），在 DMSO-d6 溶液中表征为 II 型β-转角，并通过竞争性结合试验作为大鼠神经元培养细胞中的多巴胺能 D2 调节剂进行测试，显示出中等微摩
• N-Methylidene[bis(trimethylsilyl)methyl]amine: the first isolable and stable monomeric methanimine allowing thermal [2 + 2] cycloadditions with ketenes
  作者：Claudio Palomo、Jesus M. Aizpurua、Marta Legido、Regina Galarza

  DOI：10.1039/a607348d

  日期：——

  N-Methylidene[bis(trimethylsilyl)methyl]amine acts as a stable methanimine synthon [CH 2 NH] equivalent in [2 + 2] cycloadditions to ketenes, generated from acid chlorides and triethylamine, to provide 4-unsubstituted β-lactams in a single step.

  N-亚甲基[双（三甲基硅基）甲基]胺作为一种稳定的甲亚胺合剂[CH 2 NH]等价物，可与由酸性氯化物和三乙胺生成的酮类发生[2 + 2]环加成反应，从而一步生成 4-未取代的β-内酰胺。
• 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.
• A Contribution to the Asymmetric Synthesis of 3-Amino β-Lactams: The Diastereoselective [2+2] Cycloaddition Reaction of Chiral Aminoketene Equivalents with Enolizable Aldehyde-Derived Imines
  作者：Claudio Palomo、Jesus M. Aizpurua、Marta Legido、Antonia Mielgo、Regina Galarza

  DOI：10.1002/chem.19970030909

  日期：1997.9

  AbstractN‐[Bis(trimethylsilyl)methyl]imines 9 show unique chemical properties when compared with conventional imines. Their reaction with optically pure aminoketenes derived from dehydrochlorination of 14 and 15 affords the corresponding 3‐amino‐4‐alkyl‐β‐lactams 16 and 17 in good yields and high diastereoselectivities. The mild deprotection of bis(trimethylsilyl)methyl‐ and phenyloxazolidinone moieties with, respectively, cerium(IV) ammonium nitrate and lithium/ammonia or hydrogen/Pd(OH)2 allows the preparation of a variety of β‐lactam antibiotic building blocks.
• 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.