(+/-)-methyl 2-isocyanobutanoate | 40846-65-9

• 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 2-isocyanobutanoate
• 英文别名: α-ethyl isocyanoacetate；methyl 2-isocyanobutanoate；methyl 2-isocyanobutyrate
• CAS: 40846-65-9
• 化学式: C₆H₉NO₂
• 分子量: 127.143
• InChiKey: NGMQJQMWFNWCKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-methyl 2-isocyanobutanoate 在 盐酸 、 氯化亚砜 、 bis(cyclohexylisocyanide)gold(I) tetrafluoroborate 、 (R)-N-methyl-N-<2-(4-morpholino)ethyl>-<1-(S)-1',2-bis(diphenylphosphino)ferrocenyl>ethylamine 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 为溶剂， 反应 86.0h， 生成 methyl (4R,5R)-4-ethyl-5-methyl-2-phenyl-1,3-oxazoline-4-carboxylate
  参考文献：
  名称：

  手性二茂铁基膦-金（I）配合物催化α-异氰基羧酸酯的不对称羟醛反应不对称合成β-羟基-α-烷基氨基酸

  摘要：

  α-异氰基羧酸甲酯（CNCH（R）COOMe：R = H，Me，Et，i-Pr）与苯甲醛或乙醛在0.5–1.0 mol％手性（氨基烷基）二茂铁基膦金（I ）配合物以定量收率得到具有高对映选择性的旋光的4-甲氧基羰基-4,5-二烷基-2-恶唑啉。恶唑啉被转化成旋光的β-羟基-α-烷基氨基酸甲酯。

  DOI：

  10.1016/s0040-4020(01)86034-8
• 作为产物：
  描述：

  2-氨基丁酸甲酯 在 乙酸酐 、 三乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (+/-)-methyl 2-isocyanobutanoate
  参考文献：
  名称：

  A Resource-Efficient and Highly Flexible Procedure for a Three-Component Synthesis of 2-Imidazolines

  摘要：

  A multicomponent reaction between alpha-acidic isonitriles, primary amines, and carbonyl compounds was studied using 14 different solvents. Depending on the isocyanide that was used, optimal yields for the three-component synthesis of 2H-2-imidazolines were observed in different solvents. The solvents could be used as purchased, and in situ preformation of the imine was not required. By selecting the appropriate solvent, it was possible to considerably expand the range of compatible isocyanides toward less alpha-acidic isocyanides. Further process simplification was achieved by performing the reaction at higher concentrations and avoiding purification by column chromatography, resulting in a fast, easy to perform, and resource-efficient protocol for this three-component reaction.

  DOI：

  10.1021/jo070840x

文献信息

• Scope and Limitations of an Efficient Four-Component Reaction for Dihydropyridin-2-ones
  作者：Rachel Scheffelaar、Monica Paravidino、Anass Znabet、Rob F. Schmitz、Frans J. J. de Kanter、Martin Lutz、Anthony L. Spek、Célia Fonseca Guerra、F. Matthias Bickelhaupt、Marinus B. Groen、Eelco Ruijter、Romano V. A. Orru

  DOI：10.1021/jo902613j

  日期：2010.3.5

  4-dihydropyridin-2-ones could be prepared using a four-component reaction between phosphonates, nitriles, aldehydes, and isocyanoacetates. The reaction involves initial formation of a 1-azadiene intermediate which is trapped in situ by an isocyanoacetate to give the desired heterocyclic scaffold through cyclocondensation. The full scope and limitations of this four-component reaction are described. Variation of the

  使用膦酸酯，腈，醛和异氰基乙酸酯之间的四组分反应，可以制备范围广泛的异腈官能化3,4-二氢吡啶-2-酮。该反应涉及初始形成1-氮杂二烯中间体，其被异氰基乙酸酯原位捕获，从而通过环缩合得到所需的杂环骨架。描述了该四组分反应的全部范围和局限性。丁腈和醛输入的变化被证明是可能的，但是膦酸酯输入的变化仍然受到限制。关于异氰基乙酸酯，α-芳基异氰基乙酸酯给出中等至高的产率，并导致对3，4-顺式的完全非对映选择性。异构体。α-烷基异氰基乙酸酯以中等收率得到相应的二氢吡啶-2-酮，其中大多数为非对映异构体的混合物。环缩合过程中升高的温度通常会提高收率，并导致非对映异构体比例发生变化，有利于顺式-非对映异构体。除了异氰基乙酸酯以外，有限数量的其他α-酸性酯还导致二氢吡啶-2-酮的形成，尽管收率要低得多。计算研究表明，观察到的产率差异不能简单地与不同α-酸性酯的特定物理性质（包括酸度）相关。
• Regioselective Synthesis of Pyrroles from Alkyne-Isocyanide Click Reactions: An Angle Strain-Induced Bond Migration Approach
  作者：Jimil George、Hun Young Kim、Kyungsoo Oh

  DOI：10.1002/adsc.201601017

  日期：2016.12.7

  direct regioselective synthesis of highly functionalized pyrroles with two different electron‐withdrawing groups has been developed using an angle strain‐induced 1,2‐shift of an electron‐withdrawing group in 2H‐pyrroles. The preferential migration aptitude of an electron‐withdrawing group over alkyl and aryl groups is believed to be the result of the orbital overlap between the internal alkene and the

  利用在2个H吡咯中的吸电子基团的角应变诱导的1,2-位移，开发了具有两个不同的吸电子基团的高度官能化吡咯的直接区域选择性合成方法。吸电子基团优先于烷基和芳基的迁移能力被认为是内部烯烃与吸电子基团之间轨道重叠的结果。新开发的吡咯区域选择性合成具有广泛的底物范围，简单的反应设置和高收率（60-82％），捕获了炔烃-异氰“点击”反应的本质。
• Thiophene derivative and process for preparing the same
  申请人：Tanabe Seiyaku Co., Ltd.

  公开号：US04857543A1

  公开（公告）日：1989-08-15

  A thiophen derivative of the formula: ##STR1## wherein R.sup.1, and R.sup.2 and R.sup.3 are a lower alkyl group, Ring A is phenyl, a lower alkylenedioxy-substituted phenyl, a phenyl group having 1 to 3 substituent(s) selected from the group consisting of a lower alkyl group, a lower alkylthio group, a lower alkoxy group, a phenyl-lower alkoxy group, a lower alkoxycarbonyl group, a halogen atom, amino group and hydroxy group, X is --OCO--, --O-- or --S--, m and n are an integer of zero or 1, and p and q are an integer of zero, 1 or 2, or a salt thereof.

  一种硫代噻吩衍生物的化学式：##STR1## 其中 R.sup.1、R.sup.2 和 R.sup.3 是较低的烷基基团，环A 是苯基，一个带有较低烷二氧基取代的苯基，一个苯基，其具有1到3个取代基，所选取自较低烷基基团、较低烷硫基团、较低烷氧基团、苯基-较低烷氧基团、较低烷氧羰基团、卤素原子、氨基和羟基，X 是--OCO--、--O--或--S--，m 和 n 是零或1的整数，p 和 q 是零、1或2的整数，或其盐。
• Asymmetric aldol reaction of α-isocyanocarboxylates with paraformaldehyde catalyzed by chiral ferrocenylphosphine-gold(I) complexes: Catalytic asymmetric synthesis of α-alkylserines
  作者：Yoshihiko Ito、Masaya Sawamura、Eiji Shirakawa、Keiichi Hayashizaki、Tamio Hayashi

  DOI：10.1016/s0040-4039(00)80063-5

  日期：1988.1

  Aldol reaction of methyl α-isocyanocarboxylates (CNCH(R)COOMe: R = H, Me, Et, -Pr, Ph) with paraformaldehyde in the presence of 1 mol% of a chiral (aminoalkyl)ferrocenylphosphine-gold(I) complex gave optically active 4-alkyl-2-oxazoline-4-carboxylates (up to 83% ee) which were readily hydrolyzed to α-alkylserines.

  在1摩尔％的手性（氨基烷基）二茂铁基膦-金（I）络合物的存在下，α-异氰基羧酸甲酯（CNCH（R）COOMe：R = H，Me，Et，-Pr，Ph）与低聚甲醛的羟醛反应旋光的4-烷基-2-恶唑啉-4-羧酸盐（至多83％ee），它们很容易水解为α-烷基丝氨酸。
• A Multicomponent Reaction Towards<i>N</i>-(Cyanomethyl)amides
  作者：Niels Elders、Eelco Ruijter、Frans J. J. de Kanter、Elwin Janssen、Martin Lutz、Anthony L. Spek、Romano V. A. Orru

  DOI：10.1002/chem.200900785

  日期：2009.6.15

  Diversity‐oriented synthesis: The multicomponent reaction of α‐isocyano amides, aldehydes or ketones, and amines affords N‐(cyanomethyl)amides, presenting the fourth class of products from this combination of reagents (see scheme). The scope of the reaction is very broad and various functional groups are tolerated. The outcome of the reaction can also be directed to the formation of 2H‐2‐imidazolines

  面向多样性的合成：α-异氰基酰胺，醛或酮与胺的多组分反应提供N-（氰基甲基）酰胺，这是该试剂组合的第四类产品（请参阅方案）。反应的范围非常广泛，并且可以容忍各种官能团。反应的结果还可以通过Ag I催化直接形成2 H -2-咪唑啉。