(4S)-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]-oxazolidin-2-one | 243121-08-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S)-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]-oxazolidin-2-one
• 英文别名: (S)-4-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]oxazolidin-2-one；(4S)-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]oxazolidin-2-one；3-(E-enoyl)-1,3-oxazolidin-2-one；(4S)-3-(4,4,4-Trifluorocrotonoyl)-4beta-benzyloxazolidine-2-one；(4S)-4-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]-1,3-oxazolidin-2-one
• CAS: 243121-08-6
• 化学式: C₁₄H₁₂F₃NO₃
• 分子量: 299.249
• InChiKey: YJZFRJWNPXLOQS-MLRMMBSGSA-N

物化性质

• 沸点：
  368.6±52.0 °C(Predicted)
• 密度：
  1.360±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  L-丙氨酸甲酯盐酸盐 、 (4S)-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]-oxazolidin-2-one 在 2,4,6-三甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以90%的产率得到
  参考文献：
  名称：

  Synthesis of Partially Modified Retro and Retroinverso ψ[NHCH(CF₃)]-Peptides

  摘要：

  Asymmetric conjugate additions of chiral alpha-amino esters to chiral 4-CF3 Michael-acceptors were exploited to prepare a small library of enantiomerically pure partially modified retropeptides having a psi[NHCH(CF3)] unit as a possible mimic of the classical psi(NHCO) retropeptide unit. Yields were nearly quantitative, and the stereoselectivity, which is controlled mainly by the nitrogen nucleophile, was progressively higher with increasing the steric bulk of the alpha-amino ester side-chain R-1.

  DOI：

  10.1021/ol005876p
• 作为产物：
  描述：

  (E)-4,4,4-trifluorobut-2-enoyl chloride 、 (S)-4-苄基-2-唑烷酮 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 6.5h， 以89%的产率得到(4S)-benzyl-3-[(E)-4,4,4-trifluorobut-2-enoyl]-oxazolidin-2-one
  参考文献：
  名称：

  Michael addition of organocopper species to 3-[(E)-4,4,4-trifluorobut-2-enoyl]oxazolidin-2-ones

  摘要：

  Investigation of Michael addition has been carried out using versatile organomagnesium or lithium reagents in the presence of copper(I) species towards chiral 3-[(E)-4,4,4-trifluorobut-2-enoyl] oxazolidin-2-ones, and it was demonstrated that this route enabled us to successfully construct optically active molecules with a CF3 moiety at the chiral center in good yields as well as the high level of diastereofacial selectivity. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-1139(99)00034-2

文献信息

• Parallel Solid-Phase Synthesis of Partially Modified Retro and Retro-Inverso ψ[NHCH(CF3)]-Gly Peptides
  作者：Monica Sani、Pierfrancesco Bravo、Alessandro Volonterio、Matteo Zanda

  DOI：10.1135/cccc20021305

  日期：——

  The parallel solid-phase synthesis of small libraries of molecules belonging to a novel class of retro and retro-inverso peptides having a ψ[NHCH(CF₃)] surrogate of the conventional retro-peptide bond (NH-CO) has been accomplished. Key step for the synthesis of the -NHCH(CF₃)- unit is a Michael-type N-addition of resin bound α-amino acid esters H-AA¹-OWang (1), dipeptide H-Val-Gly-OWang (8), and tripeptide H-Val-Val-Ala-OWang (12) to (S)-3-(E-enoyl)-1,3-oxazolidin-2-one (3), which took place very effectively under mild condition. Chemoselective exocyclic oxazolidinone cleavage, followed by parallel couplings of the resulting polymer-bound pseudopeptides WangO-AA¹-ψ[NHCH(CF₃)]-Gly-OH (5), WangO-Gly-Val-ψ[NHCH(CF₃)]-Gly-OH (10), and WangO-Ala-Val-Val-ψ[NHCH(CF₃)]-Gly-OH (14) with different α-amino acid esters afforded, after release from the resin, a representative set of ψ[NHCH(CF₃)] retro and retro-inverso tripeptides HO-AA¹-ψ[NHCH(CF₃)]-Gly-AA²-OX¹ (7), tetrapeptides HO-Gly-Val-ψ[NHCH(CF₃)]-Gly-AA³-OX² (11), and pentapeptides HO-Ala-Val-Val-ψ[NHCH(CF₃)]-Gly-AA⁴-OX³ (15), respectively, with good to excellent purity in all cases.

  这种新型类别的retro和retro-inverso肽分子的小型分子库的并行固相合成已经完成。合成-NHCH(CF3)-单元的关键步骤是树脂结合α-氨基酸酯H-AA1-OWang（1）、二肽H-Val-Gly-OWang（8）和三肽H-Val-Val-Ala-OWang（12）与（S）-3-（E-烯酰基）-1,3-噁唑烷-2-酮（3）的Michael型N-加成，在温和条件下非常有效地进行。化学选择性的外环氧噁唑烷酮裂解，随后将所得的聚合物结合的假肽WangO-AA1-ψ[NHCH(CF3)]-Gly-OH（5）、WangO-Gly-Val-ψ[NHCH(CF3)]-Gly-OH（10）和WangO-Ala-Val-Val-ψ[NHCH(CF3)]-Gly-OH（14）与不同的α-氨基酸酯并行偶联，在从树脂中释放后，分别获得了一组代表性的ψ[NHCH(CF3)] retro和retro-inverso三肽HO-AA1-ψ[NHCH(CF3)]-Gly-AA2-OX1（7）、四肽HO-Gly-Val-ψ[NHCH(CF3)]-Gly-AA3-OX2（11）和五肽HO-Ala-Val-Val-ψ[NHCH(CF3)]-Gly-AA4-OX3（15），在所有情况下纯度良好至优良。
• Asymmetric synthesis of chiral trifluoromethylated heliotridane via highly catalytic asymmetric Friedel–Crafts alkylation with β-trifluoromethylated acrylates and pyrroles
  作者：Yiyong Huang、Satoru Suzuki、Guokai Liu、Etsuko Tokunaga、Motoo Shiro、Norio Shibata

  DOI：10.1039/c1nj20550a

  日期：——

  Chiral Ph-dbfox (Ph-dbfox = (R,R)-4,6-dibenzofurandiyl-2,2′-bis(4-phenyloxazoline))/Zn(NTf2)2 catalyzed enantioselective Friedel–Crafts reactions of β-CF3 acrylates with pyrroles and indoles have been investigated, which afforded the corresponding chiral trifluoromethyl pyrrole and indole derivatives in high yields (90–99%) with a range of 66–99% ee values. With the aid of the chiral adduct of the asymmetric Friedel–Crafts reaction, the chiral trifluoromethylated heliotridane has been successfully constructed in good total yield.

  研究了由手性Ph-dbfox (Ph-dbfox = (R,R)-4,6-二苯并呋喃二基-2,2'-双(4-苯氧噁唑)）/Zn(NTf2)2 催化的enantioselective Friedel–Crafts反应，其中β-CF3丙烯酸酯与吡咯和吲哚反应，得到了相应的手性三氟甲基吡咯和吲哚衍生物，产率高达90-99%，光学纯度（ee值）范围为66-99%。借助于不对称Friedel–Crafts反应的手性加成物，成功合成了手性三氟甲基化的海特立烷，且总产率良好。
• Enantioselective Friedel−Crafts Reaction of β-Trifluoromethylated Acrylates with Pyrroles and Its Application to the Synthesis of Trifluorinated Heliotridane
  作者：Yiyong Huang、Etsuko Tokunaga、Satoru Suzuki、Motoo Shiro、Norio Shibata

  DOI：10.1021/ol100171z

  日期：2010.3.5

  The first chiral Lewis acid catalyzed enantioselective Friedel−Crafts alkylation of pyrroles with β-CF3 acrylates has been investigated, which afforded various types of chiral trifluoromethylated compounds in excellent yields (90−99%) with high ee’s (up to 99% ee). With the aid of the Friedel−Crafts reaction adduct, optically active trifluorinated heliotridane was successfully constructed.

  第一手性路易斯酸催化的吡咯的对映选择性的Friedel-Crafts烷基化β-CF 3个丙烯酸酯已被研究，得到各种类型的手性化合物三氟甲基化以优良产率（90-99％）与高ee值的（高达99％ee）的。借助Friedel-Crafts反应加合物，成功构建了具有光学活性的三氟化三碘d烷。
• Synthesis, Structure and Conformation of Partially-Modified Retro- and Retro-Inversoψ[NHCH(CF3)]Gly Peptides
  作者：Alessandro Volonterio、Stefano Bellosta、Fabio Bravin、Maria Cristina Bellucci、Luca Bruché、Giorgio Colombo、Luciana Malpezzi、Stefania Mazzini、Stefano V. Meille、Massimiliano Meli、Carmen Ramírez de Arellano、Matteo Zanda

  DOI：10.1002/chem.200304881

  日期：2003.9.22

  sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state

  psi [NHCH（CF（3））] Gly肽，部分概念修饰的逆肽（PMR）和逆反（PMRI）肽，是一类概念上新型的拟肽，已通过Aza-Michael反应合成了宽结构多样性和可变长度的肽对映体纯的α-氨基酯和对映体和几何纯的N-4,4,4-三氟巴豆酰基-恶唑烷-2-酮。已经研究了观察到的中等到良好非对映控制的基础因素。已通过溶液的MD计算支持（1）H NMR光谱研究了溶液中模型PMR-psi [NHCH（CF（3））] Gly三肽的构象，并通过X射线衍射研究了其固态。可以证明，与亲本基于丙二酰基的逆向肽相比，turn-like构象具有显着的稳定性，这可能是由于以下两个主要因素造成的：1）对[CO-CH（2）-CH（CF（3））-NH-CH（R）-CO]模块中sp（3）键的严格扭转限制，这受立体电子要求的CF（3）的偏见）基团和R侧链；2）形成的九元分子内氢键环，已经清楚地在CHCl（3）溶液
• 10.1002/1099-0690(20022)2002:3<428::aid-ejoc428<3.0.co;2-j
  作者：Volonterio, Alessandro、Bellosta, Stefano、Bravo, Pierfrancesco、Canavesi, Monica、Corradi, Eleonora、Meille, Stefano V.、Monetti, Mara、Moussier, Nathalie、Zanda, Matteo

  DOI：10.1002/1099-0690(20022)2002:3<428::aid-ejoc428<3.0.co;2-j

  日期：——