4-benzyl-2-(4-methoxyphenyl)oxazol-5(4H)-one | 217446-35-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4-benzyl-2-(4-methoxyphenyl)oxazol-5(4H)-one
• 英文别名: 4-benzyl-2-(4-methoxyphenyl)-4H-1,3-oxazol-5-one
• CAS: 217446-35-0
• 化学式: C₁₇H₁₅NO₃
• 分子量: 281.311
• InChiKey: VHFMHHSKQIRCQX-UHFFFAOYSA-N

物化性质

• 沸点：
  409.9±47.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-benzyl-2-(4-methoxyphenyl)oxazol-5(4H)-one 在 2-phenyl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate 、 双(三甲基硅烷基)氨基钾 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 4-benzyl-5-oxo-2-(4-methoxyphenyl)-4,5-dihydrooxazole-4-carboxylic acid methyl ester
  参考文献：
  名称：

  Efficient N-Heterocyclic Carbene-Catalyzed O- to C-Acyl Transfer

  摘要：

  An N-heterocyclic carbene promotes the rearrangement of alpha-amino acid derived O-acyl carbonates to their corresponding C-acylated isomers, generating a C-C bond and a quaternary stereocenter with high efficiency, under mild reaction conditions and with low catalyst loadings.

  DOI：

  10.1021/ol061380h
• 作为产物：
  描述：

  DL-苯基丙氨酸甲酯盐酸盐 在 三乙胺 、 N,N'-二环己基碳二亚胺 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 4-benzyl-2-(4-methoxyphenyl)oxazol-5(4H)-one
  参考文献：
  名称：

  Regiodivergent Enantioselective γ-Additions of Oxazolones to 2,3-Butadienoates Catalyzed by Phosphines: Synthesis of α,α-Disubstituted α-Amino Acids and N,O-Acetal Derivatives

  摘要：

  Phosphine-catalyzed regiodivergent enantioselective C-2- and C-4-selective gamma-additions of oxazolones to 2,3-butadienoates have been developed. The C-4-selective gamma-addition of oxazolones occurred in a highly enantioselective manner when 2-aryl-4-alkyloxazol-5-(4H)-ones were employed as pronudeophiles. With the employment of 2-alkyl-4-aryloxazol-5-(4H)-ones as the donor, C-2-selective gamma-addition of oxazolones took place in a highly enantioselective manner. The C-4-selective adducts provided rapid access to optically enriched alpha,alpha-disubstituted alpha-amino acid derivatives, and the C-2-selective products led to facile synthesis of chiral N,O-acetals and gamma-lactols. Theoretical studies via DFT calculations suggested that the origin of the observed regioselectivity was due to the distortion energy that resulted from the interaction between the nudeophilic oxazolide and the electrophilic phosphonium intermediate.

  DOI：

  10.1021/jacs.5b10524

文献信息

• Enantioselective TADMAP-Catalyzed Carboxyl Migration Reactions for the Synthesis of Stereogenic Quaternary Carbon
  作者：Scott A. Shaw、Pedro Aleman、Justin Christy、Jeff W. Kampf、Porino Va、Edwin Vedejs

  DOI：10.1021/ja056150x

  日期：2006.1.1

  efficient and are used to prepare chiral lactams (23) and lactones (30) containing a quaternary asymmetric carbon. TADMAP-catalyzed carboxyl migrations in the indole series are relatively slow and proceed with inconsistent enantioselectivity. Modeling studies (B3LYP/6-31G*) have been used in qualitative correlations of catalyst conformation, reactivity, and enantioselectivity.

  手性亲核催化剂 TADMAP [1, 3-(2,2,2-三苯基-1-乙酰氧基乙基)-4-(二甲氨基)吡啶]已由 3-锂硫-4-(二甲氨基)吡啶 (5) 和三苯乙醛 (3)，然后进行酰化和拆分。TADMAP 催化恶唑基、呋喃基和苯并呋喃基烯醇碳酸酯的羧基迁移，具有良好到极好的对映选择水平。恶唑反应特别有效，用于制备含有季不对称碳的手性内酰胺 (23) 和内酯 (30)。吲哚系列中 TADMAP 催化的羧基迁移相对较慢，并且具有不一致的对映选择性。建模研究 (B3LYP/6-31G*) 已用于定性关联催化剂构象、反应性和对映选择性。
• Enantioselective [4 + 2]-Annulation of Azlactones with Copper-Allenylidenes under Cooperative Catalysis: Synthesis of α-Quaternary α-Acylaminoamides
  作者：Amit Kumar Simlandy、Biki Ghosh、Santanu Mukherjee

  DOI：10.1021/acs.orglett.9b01103

  日期：2019.5.3

  enantioselective decarboxylative [4 + 2]-annulation of ethynyl benzoxazinanones with azlactones has been developed under cooperative copper and bifunctional tertiary aminourea catalysis. This direct and modular approach combines dipolar copper-allenylidene intermediates with azlactone enolates and allows for the synthesis of α-quaternary α-acylaminoamides as a single diastereomer generally in high yields

  乙炔基苯并恶嗪酮与氮杂内酯的首次对映选择性脱羧[4 + 2]-环化反应是在铜和双功能叔氨基脲协同催化下进行的。这种直接的模块化方法将偶极铜-亚烯基中间体与氮杂内酯烯醇酸酯结合在一起，并允许以高收率和良好至出色的对映选择性（高达99：1 er）合成高纯度的α-季α-酰基氨基酰胺。
• Amidine catalysed O- to C-carboxyl transfer of heterocyclic carbonate derivatives
  作者：Caroline Joannesse、Carmen Simal、Carmen Concellón、Jennifer E. Thomson、Craig D. Campbell、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1039/b805850d

  日期：——

  The structural requirements of amidines necessary to act as efficient O- to C-carboxyl transfer agents are delineated and the scope of this process outlined through its application to a range of oxazolyl, benzofuranyl and indolyl carbonates.

  为了成为有效的O向C羧基转移剂，胍基的结构要求被阐明，并通过应用于一系列噁唑基、苯并呋喃基和吲哚基碳酸酯来概述该过程的范围。
• Asymmetric Synthesis of 3,4-Diaminochroman-2-ones Promoted by Guanidine and Bisguanidium Salt
  作者：Shunxi Dong、Xiaohua Liu、Yulong Zhang、Lili Lin、Xiaoming Feng

  DOI：10.1021/ol2018888

  日期：2011.10.7

  A highly enantioselective synthesis of 3,4-diaminochroman-2-ones has been realized via the domino reaction of o-hydroxy aromatic aldimines and azlactones. Notably, a cis-product was obtained as the major product by the use of guanidine 2a whereas a trans-product was the major product with bisguanidium salt 3•HBArF4. In two cases, various substituted 3,4-dihydrocoumarins were obtained with high yields

  通过邻羟基芳族醛亚胺和a内酯的多米诺反应，已经实现了对3,4-二氨基苯并二氢吡喃-2-酮的高度对映选择性的合成。值得注意的是，通过使用胍2a获得了顺式产物作为主要产物，而反式产物是双胍盐3•HBAr F 4的主要产物。在两种情况下，以高收率（高达99％），出色的对映选择性（高达99％ee）和非对映选择性（高达> 99：1顺式：反式和98：2 ）获得了各种取代的3,4-二氢香豆素。反式：顺式，分别）在温和的反应条件下。
• Catalytic, Enantioselective α‐Alkylation of Azlactones with Nonconjugated Alkenes by Directed Nucleopalladation
  作者：Sri Krishna Nimmagadda、Mingyu Liu、Malkanthi K. Karunananda、De‐Wei Gao、Omar Apolinar、Jason S. Chen、Peng Liu、Keary M. Engle

  DOI：10.1002/anie.201814272

  日期：2019.3.18

  palladium(II)‐catalyzed enantioselective α‐alkylation of azlactones with nonconjugated alkenes is described. The reaction employs a chiral BINOL‐derived phosphoric acid as the source of stereoinduction, and a cleavable bidentate directing group appended to the alkene to control the regioselectivity and stabilize the nucleopalladated alkylpalladium(II) intermediate in the catalytic cycle. A wide range of

  描述了钯（II）催化的内酯与非共轭烯烃的对映选择性α-烷基化。该反应使用手性BINOL衍生的磷酸作为立体诱导的来源，并且在烯烃上附加了可裂解的双齿导向基团，以控制区域选择性并稳定催化循环中的核钯烷基钯（II）中间体。人们发现，在最佳反应条件下，各种各样的内酯都具有相容性，从而能够以高收率和高对映选择性提供带有α，α-二取代的α-氨基酸衍生物的产物。