methyl 4-cyano-3-methylpentanoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 4-cyano-3-methylpentanoate
• 英文别名: Methyl 4-cyano-3-methylpentanoate
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: IRYVJINXNQOVRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  巴豆酸甲酯 、 丙腈 在 C₂₅H₄₂MnNO₂P₂ 作用下， 以 neat (no solvent) 为溶剂， 反应 24.0h， 以18%的产率得到methyl 4-cyano-3-methylpentanoate
  参考文献：
  名称：

  [EN] MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
  [FR] COMPLEXES À BASE DE MANGANÈSE ET LEURS UTILISATIONS SERVANT À UNE CATALYSE HOMOGÈNE

  摘要：

  本发明涉及新型锰配合物及其用途，包括但不限于在以下领域进行均相催化：（1）通过醇和胺的脱氢偶联制备亚胺；（2）使用腈作为迈克尔供体进行迈克尔加成反应中的C-C偶联；（3）将醇脱氢偶联以得到酯和氢气；（4）将酯加氢以形成醇（包括环酯（内酯）或环二酯（二内酯）或聚酯的加氢）；（5）将酰胺（包括环二肽、内酰胺、二酰胺、多肽和聚酰胺）加氢以得到醇和胺（或二胺）；（6）将有机碳酸酯（包括聚碳酸酯）加氢以得到醇或将氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物加氢以得到醇和胺；（7）将二级醇脱氢以得到酮；（8）酯的酰胺化（即从酯和胺合成酰胺）；（9）使用酯对醇进行酰化；（10）将醇与水和碱偶联以形成羧酸；以及（11）通过氨基醇与水和碱的偶联制备氨基酸或其盐。（12）通过醇和胺的脱氢偶联制备酰胺（包括甲酰胺、环二肽、二酰胺、内酰胺、多肽和聚酰胺）；（13）从二醇制备酰亚胺。

  公开号：

  WO2017137984A1

文献信息

• Template Catalysis by Metal–Ligand Cooperation. C–C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex
  作者：Alexander Nerush、Matthias Vogt、Urs Gellrich、Gregory Leitus、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/jacs.5b13208

  日期：2016.6.8

  The first example of a catalytic Michael addition reaction of non-activated aliphatic nitriles to α,β-unsaturated carbonyl compounds under mild, neutral conditions is reported. A new de-aromatized pyridine-based PNP pincer complex of the Earth-abundant, first-row transition metal manganese serves as the catalyst. The reaction tolerates a variety of nitriles and Michael acceptors with different steric

  报道了在温和、中性条件下非活化脂肪腈与 α,β-不饱和羰基化合物的催化迈克尔加成反应的第一个例子。地球丰富的第一排过渡金属锰的一种新的脱芳构化吡啶基 PNP 钳形配合物用作催化剂。该反应耐受具有不同空间特征和受体强度的各种腈和迈克尔受体。包括温度依赖性 NMR 光谱和 DFT 计算在内的机理研究表明，烷基腈的协同活化导致金属化腈亲核物质（α-氰基碳负离子类似物）的产生，是该机制的关键步骤。金属中心不直接参与催化键的形成，而是与配体合作，作为底物活化的模板。这种“模板催化”方法扩大了共轭加成反应的潜在供体范围。
• MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
  申请人：Yeda Research and Development Co. Ltd

  公开号：EP3919466A1

  公开（公告）日：2021-12-08

  The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

  本发明涉及新型锰络合物及其在以下方面的均相催化等用途：(1)通过醇和胺的脱氢偶联制备亚胺；(2)在迈克尔加成反应中使用腈作为迈克尔供体的C-C偶联；(3) 醇的脱氢偶联生成酯和氢气 (4) 酯的氢化生成醇（包括环酯（内酯）或环二酯（二内酯）或聚酯的氢化）；(5) 将酰胺（包括环状二肽、内酰胺、二酰胺、多肽和多酰胺）氢化成醇和胺（或 二胺）；(6) 将有机碳酸盐（包括聚碳酸酯）氢化成醇，或将氨基甲酸酯（包括聚氨基甲 酸酯）或脲衍生物氢化成醇和胺；(7) 将仲醇脱氢成酮；(8) 酯的酰胺化（即酰胺化）。e.,(10) 醇与水和碱偶联生成羧酸；以及 (11) 通过氨基醇与水和碱偶联制备氨基酸或其盐。(12) 通过醇和胺的脱氢偶联制备酰胺（包括甲酰胺、环二肽、二酰胺、内酰胺、多肽和多酰胺）； (13) 利用二元醇制备亚胺。
• [EN] MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS<br/>[FR] COMPLEXES À BASE DE MANGANÈSE ET LEURS UTILISATIONS SERVANT À UNE CATALYSE HOMOGÈNE
  申请人：YEDA RES & DEV

  公开号：WO2017137984A1

  公开（公告）日：2017-08-17

  The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

  本发明涉及新型锰配合物及其用途，包括但不限于在以下领域进行均相催化：（1）通过醇和胺的脱氢偶联制备亚胺；（2）使用腈作为迈克尔供体进行迈克尔加成反应中的C-C偶联；（3）将醇脱氢偶联以得到酯和氢气；（4）将酯加氢以形成醇（包括环酯（内酯）或环二酯（二内酯）或聚酯的加氢）；（5）将酰胺（包括环二肽、内酰胺、二酰胺、多肽和聚酰胺）加氢以得到醇和胺（或二胺）；（6）将有机碳酸酯（包括聚碳酸酯）加氢以得到醇或将氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物加氢以得到醇和胺；（7）将二级醇脱氢以得到酮；（8）酯的酰胺化（即从酯和胺合成酰胺）；（9）使用酯对醇进行酰化；（10）将醇与水和碱偶联以形成羧酸；以及（11）通过氨基醇与水和碱的偶联制备氨基酸或其盐。（12）通过醇和胺的脱氢偶联制备酰胺（包括甲酰胺、环二肽、二酰胺、内酰胺、多肽和聚酰胺）；（13）从二醇制备酰亚胺。