methyl 3'-nitro-α-acetamidocinnamate | 556828-91-2

• 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: methyl 3'-nitro-α-acetamidocinnamate
• 英文别名: (Z)-methyl 2-acetamido-3-(3-nitrophenyl)acrylate；methyl (Z)-2-acetamido-3-(3-nitrophenyl)prop-2-enoate
• CAS: 556828-91-2
• 化学式: C₁₂H₁₂N₂O₅
• 分子量: 264.238
• InChiKey: ZLBJDEYEQUCBFZ-XFFZJAGNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3'-nitro-α-acetamidocinnamate 在 palladium on activated charcoal 哌啶 、 吡啶 、 盐酸 、 甲醇 、 copper(l) iodide 、 四(三苯基膦)钯 、 氢气 、 sodium 、 potassium iodide 、 sodium nitrite 作用下， 反应 24.5h， 生成 N-acetyl 3-C-(3,7-anhydro-1,1,2,2-tetradehydro-1,2-D-glycero-D-mannooctityl)-DL-phenylalanine
  参考文献：
  名称：

  Novel Type of Rigid C-Linked Glycosylacetylene−Phenylalanine Building Blocks for Combinatorial Synthesis of C-linked Glycopeptides

  摘要：

  C-linked 3- and 4-(glycosylacetylene)-Fmoc-phenylalanines were synthesized as rigid building blocks for synthesis of libraries of neoglycopeptide templates. Perbenzylated 1,5-galactonolactone, 1,5-gluconolactone, and 1,5-mannonolactone were reacted with cerium TMS-acetylide and the products reduced to the C-glycosylacetylene-TMS derivatives. The gluco and galacto configurations yielded exclusively the beta-C-glycoside, whereas the mannonolactone gave a mixture of alpha-C- and beta-C-anomer. The products were subjected to acetolysis and TMS cleavage. The resulting peracetylated glycosylacetylenes were cross-coupled with the (R,S)-N-alpha-acetyl-3- and 4-iodophenylalanine O-methyl esters by Pd(0) catalysis in piperidine to give the eight possible C-linked glycosyl amino acid building blocks 33-40 as diastereomeric pairs. These were O-deacetylated. As an example of further conversion into neoglycopeptide templates the N-acetyl group of the 4-linked galacto-diastereomeric pair 43 was hydrolyzed selectively by acylase 1 and separated from the (R)stereoisomer. The product was converted to 4-(beta-C-galactosylacetylene)(N-alpha-Fmoc-)-L-phenylalanine (52) by reaction with Fmoc-OSu. Acid hydrolysis of galactosyl acetylene phenyl alanine 43 at elevated temperature afforded the conversion of the acetylene to the 1'-oxo derivative which was also N-alpha-Fmoc protected. The building blocks were used in the glycopeptide synthesis of three neoglycopeptide templates 54, 55, and 56 known to bind to murine MHC class II E-k and to present the glycan for interaction with the T-cell receptor. This template has previously been employed to elicit a carbohydrate specific T-cell response.

  DOI：

  10.1021/jo980517h
• 作为产物：
  描述：

  甲醇 、 2-methyl-4-[(3-nitrophenyl)methyl]-4H-1,3-oxazol-5-one 反应 9.0h， 生成 methyl 3'-nitro-α-acetamidocinnamate
  参考文献：
  名称：

  Novel Type of Rigid C-Linked Glycosylacetylene−Phenylalanine Building Blocks for Combinatorial Synthesis of C-linked Glycopeptides

  摘要：

  C-linked 3- and 4-(glycosylacetylene)-Fmoc-phenylalanines were synthesized as rigid building blocks for synthesis of libraries of neoglycopeptide templates. Perbenzylated 1,5-galactonolactone, 1,5-gluconolactone, and 1,5-mannonolactone were reacted with cerium TMS-acetylide and the products reduced to the C-glycosylacetylene-TMS derivatives. The gluco and galacto configurations yielded exclusively the beta-C-glycoside, whereas the mannonolactone gave a mixture of alpha-C- and beta-C-anomer. The products were subjected to acetolysis and TMS cleavage. The resulting peracetylated glycosylacetylenes were cross-coupled with the (R,S)-N-alpha-acetyl-3- and 4-iodophenylalanine O-methyl esters by Pd(0) catalysis in piperidine to give the eight possible C-linked glycosyl amino acid building blocks 33-40 as diastereomeric pairs. These were O-deacetylated. As an example of further conversion into neoglycopeptide templates the N-acetyl group of the 4-linked galacto-diastereomeric pair 43 was hydrolyzed selectively by acylase 1 and separated from the (R)stereoisomer. The product was converted to 4-(beta-C-galactosylacetylene)(N-alpha-Fmoc-)-L-phenylalanine (52) by reaction with Fmoc-OSu. Acid hydrolysis of galactosyl acetylene phenyl alanine 43 at elevated temperature afforded the conversion of the acetylene to the 1'-oxo derivative which was also N-alpha-Fmoc protected. The building blocks were used in the glycopeptide synthesis of three neoglycopeptide templates 54, 55, and 56 known to bind to murine MHC class II E-k and to present the glycan for interaction with the T-cell receptor. This template has previously been employed to elicit a carbohydrate specific T-cell response.

  DOI：

  10.1021/jo980517h

文献信息

• Ni(<scp>ii</scp>)-Catalyzed vinylic C–H functionalization of 2-acetamido-3-arylacrylates to access isotetronic acids
  作者：Biswajit Roy、Eshani Das、Avijit Roy、Dipakranjan Mal

  DOI：10.1039/d0ob00557f

  日期：——

  reaction for the synthesis of 4-aryl-substituted isotetronic acids from 2-acetamido-3-arylacrylates via vinylic C-H functionalization is reported. The reaction proceeds through heteroatom guided electrophilic insertion of nickel to the vinylic double bond followed by annulation with dibromomethane. This unconventional route features cascade steps, sole product formation, multiple functional group tolerance

  报道了通过乙烯基CH官能团由2-乙酰氨基-3-芳基丙烯酸酯合成4-芳基取代的等渗酸的无配体Ni（ii）催化的级联环化反应。该反应通过镍的杂原子引导的亲电子插入到乙烯基双键中，然后用二溴甲烷环化而进行。该非常规途径具有级联步骤，单一产物形成，多官能团耐受性，催化剂和试剂的低成本以及容易获得的起始原料的特征。使用这种方法，已经合成了生物学上相关的各种芳基取代的等渗酸。还已经用1,2-二氯乙烷评估了2-乙酰氨基-3-芳基丙烯酸酯的环化，这导致了5-甲基取代的等渗酸的重排环化产物。
• Monodentate Phosphoramidites: A Breakthrough in Rhodium-Catalysed Asymmetric Hydrogenation of Olefins
  作者：Michel van den Berg、Adriaan J. Minnaard、Robert M. Haak、Michel Leeman、Ebe P. Schudde、Auke Meetsma、Ben L. Feringa、André H. M. de Vries、C. Elizabeth P. Maljaars、Charlotte E. Willans、David Hyett、Jeroen A. F. Boogers、Hubertus J. W. Henderickx、Johannes G. de Vries

  DOI：10.1002/adsc.200390026

  日期：2003.1

  ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BINOL and HMPT. Turnover numbers up to 6000 have been obtained in the hydrogenation of dehydroamino acid derivatives. Enantioselectivities in the hydrogenation of dehydroamino acids are solvent

  基于BINOL或取代BINOL的单齿亚磷酰胺是铑催化烯烃不对称氢化的出色配体。用MonoPhos（7a获得了很高的对映选择性）此类中最简单的成员，它是由BINOL和HMPT一步合成的配体。在脱氢氨基酸衍生物的氢化中，已经获得了高达6000的营业额。脱氢氨基酸加氢中的对映选择性取决于溶剂。在非质子溶剂中，它们的含量范围为95–99％。衣康酸及其二甲酯可以分别用96％ee和94％ee氢化。芳香族酰胺的氢化反应在86-94％ee中得到相应的酰化胺。已经制备了几种类似的亚磷酰胺配体。出人意料的是，就速率和对映选择性而言，双齿配体均给出较差的结果。基于Taddol的亚磷酰胺导致ee较差并降低速度。3处的甲基取代基 BINOL的3'-位置导致速率急剧降低，对映选择性略低。在6,6'-位的溴取代基导致速率略有降低，但对映选择性几乎没有影响。八氢-MonoPhos（11）得出的结果与用7a获得的结果非常相
• Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins Using Monodentate Spiro Phosphoramidite Ligands
  作者：Yu Fu、Xun-Xiang Guo、Shou-Fei Zhu、Ai-Guo Hu、Jian-Hua Xie、Qi-Lin Zhou

  DOI：10.1021/jo049655z

  日期：2004.7.1

  Novel chiral monodentate phosphorus ligands, SIPHOS, were conveniently synthesized from 1,1‘-spirobiindane-7,7‘-diol. The Rh complexes of SIPHOS can catalyze the hydrogenation of α-dehydroamino esters in mild conditions, providing α-amino acid derivatives in up to 99% ee. Enamides and β-dehydroamino esters can also be hydrogenated in good to excellent enantioselectivities (up to 99% and 94% ee, respectively)

  新型手性单齿磷配体SIPHOS是由1,1'-spirbibiindane-7,7'-diol方便地合成的。SIPHOS中Rh复合物可以催化的氢化α在温和的条件-dehydroamino酯，提供α在高达99％ee的β-氨基酸衍生物。酰胺和β-脱氢氨基酯也可以以良好至优异的对映选择性（分别高达99％和94％ee）氢化。在N原子上具有较小烷基的SIPHOS配体具有较高的对映选择性。单晶的X射线分析表明，Rh / SIPHOS催化剂的结构为[Rh（COD）（（S）-SIPHOS-Me）2 ] +，阐明了在Rh催化的不对称加氢反应中单齿手性磷配体的催化剂构型。在脱氢氨基酸衍生物的氢化中，观察到配体和产物的光学纯度之间的正非线性效应。氢化动力学研究表明，该反应在底物浓度上为零级，在Rh催化剂浓度和加氢压力下为一级。当Rh / L比从1：1变为1：4时，氢化速率降低。
• The Synthesis of Spirobitetraline Phosphoramidite Ligands and their Application in Rhodium-Catalyzed Asymmetric Hydrogenation
  作者：Xiang-Hong Huo、Jian-Hua Xie、Qiu-Shi Wang、Qi-Lin Zhou

  DOI：10.1002/adsc.200700109

  日期：2007.11.5

  synthesized from 3-methoxybenzaldehyde in 26 % yield over 9 steps and resolved via its bis-(S)-camphorsulfonates. The corresponding chiral spirobitetraline monophosphoramidite ligands have been prepared and their rhodium complexes were applied in the asymmetric hydrogenation of dehydroamino esters with good to excellent enantioselectivities (up to 99.3 % ee).

  外消旋1,1' - spiroBITetralin-8,8'-二醇（SBITOL）中的溶液方便地由3-甲氧基苯甲醛的合成在26％的产率超过9个步骤和解析经由（其双-小号）-camphorsulfonates。制备了相应的手性螺双四环联单磷酰胺基配体，并将它们的铑配合物用于对氢氨基酯的不对称加氢，具有良好至优异的对映选择性（最高99.3％ee）。
• Novel monodentate spiro phosphorus ligands for rhodium-catalyzed hydrogenation reactions
  作者：Yu Fu、Jian-Hua Xie、Ai-Guo Hu、Hai Zhou、Li-Xin Wang、Qi-Lin Zhou

  DOI：10.1039/b109827f

  日期：2002.2.27

  Novel monodentate phosphorus ligands containing the 1,1'-spirobiindane backbone have been synthesized and applied in the asymmetric rhodium-catalyzed hydrogenation of functionalized olefins, providing excellent enantioselectivities (up to 99.3% ee).

  已经合成了包含1,1'-螺双茚满主链的新型单齿磷配体，并将其用于官能化烯烃的不对称铑催化的氢化反应中，提供了出色的对映选择性（高达99.3％ee）。