methyl (Z)-α-acetamido-β-(1-naphthyl)acrylate | 131305-18-5

• 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 (Z)-α-acetamido-β-(1-naphthyl)acrylate
• 英文别名: (Z)-methyl 2-acetamido-3-(naphthalen-1-yl)acrylate；methyl (Z)-2-acetamido-3-naphthalen-1-ylprop-2-enoate
• CAS: 131305-18-5
• 化学式: C₁₆H₁₅NO₃
• 分子量: 269.3
• InChiKey: HNLYJUSTCBOAAY-GDNBJRDFSA-N

物化性质

• 沸点：
  518.3±50.0 °C(Predicted)
• 密度：
  1.206±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (Z)-α-acetamido-β-(1-naphthyl)acrylate 在 [Rh(cod)(Ph₂P(CH₂)2PO₂((S)-10,10'-binaphanthr-9-yl)]BF₄ 作用下， 以 二氯甲烷 为溶剂， 25.0 ℃ 、500.01 kPa 条件下， 反应 1.0h， 生成 (R)-N-acetyl-3-(1-naphthyl)alanine methyl ester
  参考文献：
  名称：

  不对称氢化催化中的双齿与单齿：对速率的协同效应和对映选择性的变构效应

  摘要：

  C 1-对称膦基/亚膦酸酯配体通过 Ph 2P(CH 2) 2P(NMe 2) 2 与 (S)-1,1'-bi-2-naphthol（得到 LA）或（S）的反应制备-10,10'-bi-9-phenanthrol（给 LB ）。外消旋 10,10'-bi-9-phenanthrol 是由菲以 44% 的总产率分三步合成的。配合物 [PdCl 2( LA,B )] ( 1a, b), [PtCl 2( LA,B )] ( 2a, b), [Rh(cod)( LA,B )]BF 4 ( 3a, b) [Rh(LA,B) 2]BF 4 ( 4a, b) 和[Rh( LA,B ) 2 ] BF 4 ( 4a, b) 已被报道并确定了1a 的晶体结构。(31)P NMR 研究表明 M，单齿化合物、PMePh 2 和甲基单亚膦酸酯 L 1a（基于 (S)-1,1'-bi-2-naphthol）的 1:1

  DOI：

  10.1021/ja800858x
• 作为产物：
  描述：

  1-萘甲醛 在 sodium methylate 、 sodium acetate 、 乙酸酐 作用下， 反应 5.75h， 生成 methyl (Z)-α-acetamido-β-(1-naphthyl)acrylate
  参考文献：
  名称：

  Z-α-(N-乙酰氨基)-和Z-α-(N-苯甲酰氨基)-α,β-不饱和酸的实际制备

  摘要：

  摘要 开发了一种有效的两步合成程序，用于从 N-保护的甘氨酸和脂肪族或芳香族醛制备 N-保护的 α,β-不饱和 α-氨基酸及其相应的酯的多种变体。该反应包括将 N 保护的甘氨酸环化为恶唑酮、与醛缩合以及与碱开环。

  DOI：

  10.1080/00397910701265895

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
• Design and Preparation of a Chiral Ligand Based on a Pseudorotaxane Skeleton:  Application to Rhodium-Catalyzed Enantioselective Hydrogenation of Enamides
  作者：Gaku Hattori、Tetsuharu Hori、Yoshihiro Miyake、Yoshiaki Nishibayashi

  DOI：10.1021/ja075231l

  日期：2007.10.1

  works as a chiral bidentate ligand having a phosphine moiety in an axle and a phosphite moiety in a wheel as two coordination sites and applied it successfully to the rhodium-catalyzed enantioselective hydrogenation of enamides (up to 96% ee). To the best of our knowledge, this is the first successful example of the use of the pseudorotaxane molecule as a chiral ligand for homogeneous transition-metal-catalyzed

  我们制备了一种新型假轮烷分子作为手性双齿配体，轴中有膦部分，轮中有亚磷酸酯部分作为两个配位位点，并将其成功应用于铑催化的烯酰胺的对映选择性氢化（高达 96% ee)。据我们所知，这是使用拟轮烷分子作为均相过渡金属催化的不对称反应的手性配体的第一个成功例子。
• Synthesis and Application of Phosphinoferrocenylaminophosphine Ligands for Asymmetric Catalysis
  作者：Neil W. Boaz、Elaine B. Mackenzie、Sheryl D. Debenham、Shannon E. Large、James A. Ponasik

  DOI：10.1021/jo048312y

  日期：2005.3.1

  [GRAPHICS]A new class of bidentate ligands utilizing a phosphine-aminophosphine structure has been prepared on a ferrocenylethyl backbone in a straightforward and scalable fashion from acetylferrocene. The unique property of the alpha-ferrocenyl carbonium ion that allows the replacement of a variety of "leaving groups" with retention of configuration greatly facilitates the synthesis, and a number of ligands have been prepared by varying the nitrogen and phosphorus substituents on the aminophosphine. These readily prepared phosphinoferrocenylaminophosphines, known as BoPhoz ligands, show surprising hydrolytic and air stability, with no degradation after 3 years open to the air. The rhodium complexes of these ligands show exceedingly high enantioselectivities (generally >95% ee) and activities often in excess of 50 000 catalyst turnovers per hour for the asymmetric hydrogenation of a wide variety of dehydro-alpha-amino acid and itaconic acid derivatives. They also show high activity and good to excellent enantioselectivity for the hydrogenation of a number of alpha-ketoesters.
• Highly Enantioselective Hydrogenation of Enamides and Itaconic Acid in Water in the Presence of Water-Soluble Rhodium(I) Catalyst and Sodium Dodecyl Sulfate
  作者：Koji Yonehara、Kouichi Ohe、Sakae Uemura

  DOI：10.1021/jo9912505

  日期：1999.12.1

  The water-soluble cationic Rh complexes, such as [Rh(alpha-D-glucopyranosyl-(1,1)-2,3-di-O-(diphenylphosphino)-alpha-D-glucopyranoside)(cod)]BF4 (1) and [Rh(beta-D-glucopyranosyl-(1,1)-2,3-di-O-(diphenylphosphino)-beta-D-glucopyranoside)(cod)]BF4 (2) bearing free hydroxy groups, are effective catalysts in the asymmetric hydrogenation of various enamides and itaconic acid (up to 99.9% ee) in water in the presence of sodium dodecyl sulfate (SDS) (7.5 x 10(-3) to 1.0 x 10(-1) M). The hydrogenation of methyl (Z)-alpha-acetamidocinnamate in water using the corresponding Rh complexes of triflate (6) and D-camphor-10-sulfonate (7), prepared separately, results in a formation of the product of the same enantioselectivity (48% ee), but the use of SDS can reduce the amount of the catalyst and improve the enantioselectivity to 81% ee. These results show that the counteranions do not directly influence the enantioselectivity. Although the effect of SDS on the enhancement of enantioselectivity remains speculative, the formation of micelle seems to play an important role in improving the enantioselectivity.