2-allyl-2-methylmalononitrile | 154657-02-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-allyl-2-methylmalononitrile
• 英文别名: 2-Methyl-2-prop-2-enylpropanedinitrile；2-methyl-2-prop-2-enylpropanedinitrile
• CAS: 154657-02-0
• 化学式: C₇H₈N₂
• 分子量: 120.154
• InChiKey: GOBUMHRVHCYHSC-UHFFFAOYSA-N

物化性质

• 沸点：
  238.8±20.0 °C(predicted)
• 密度：
  0.953±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-allyl-2-methylmalononitrile 在 双氧水 作用下， 生成 2-allyl-2-methylmalonamide
  参考文献：
  名称：

  微生物全细胞催化手性丙二酰胺的脱对称：富含对映体的官能化氨基甲酰乙酸酯的实际合成及其在制备异常α-氨基酸中的应用

  摘要：

  在非常温和的条件下，由含酰胺酶的微生物全细胞催化剂红球菌红球菌AJ270催化，对许多官能化的手性丙二酰胺进行对映选择性去对称化反应，以高产率得到氨基甲酰乙酸，且具有中等至优异的对映选择性。R -（-）-α-烯丙基-α-甲基氨基甲酰乙酸的多克级生物催化制备及其转化成药用目的各种α，α-二取代α-氨基酸的合成应用已得到证明化学。

  DOI：

  10.1016/j.tet.2011.05.103
• 作为产物：
  描述：

  methyliodomalononitrile 在 zinc chloride diethyl ether 、 烯丙基三丁基锡 作用下， 以 二氯甲烷 为溶剂， 以36%的产率得到2-allyl-2-methylmalononitrile
  参考文献：
  名称：

  Yamamoto, Yoshinori; Onuki, Setsuko; Yumoto, Masatoshi, Journal of the American Chemical Society, 1994, vol. 116, # 1, p. 421 - 422

  摘要：

  DOI：

文献信息

• Palladium catalysed direct allylation of pronucleophiles with allylstannanes
  作者：Yoshinori Yamamoto、Naoya Fujiwara

  DOI：10.1039/c39950002013

  日期：——

  The reaction of pronucleophiles 1 with allyltributylstannanes in the presence of catalytic amounts of Pd2(dba)3·CHCl3(4 mol%) and 1,2-bis(diphenylphosphino)ethane (dppe)(10 mol%) at room temperature gives the corresponding allylation products in good to high yields.

  在催化量的Pd2(dba)3·CHCl3(4 mol%)和1,2-双(二苯膦)乙烷(dppe)(10 mol%)存在下，室温下丙烯基三丁基锡与亲核试剂1反应，以良好至高产率得到了相应的丙烯基化产物。
• Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles
  作者：Christian A. Malapit、Donald R. Caldwell、Irungu K. Luvaga、Jonathan T. Reeves、Ivan Volchkov、Nina C. Gonnella、Zhengxu S. Han、Carl A. Busacca、Amy R. Howell、Chris H. Senanayake

  DOI：10.1002/anie.201703471

  日期：2017.6.6

  prepared through Rh‐catalyzed addition of aryl boronic acids to 2,2‐disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro‐Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted

  通过在2，2-二取代的丙二腈中Rh催化芳基硼酸的加成反应，制得了在2位带有季碳的β-乙腈。与之前描述的芳基硼酸与二烷基丙二腈的反硝化氰化相反，本反应通过使用较温和的碱避免了中间体加成产物的逆索普-索普塌缩。该反应适用于各种芳基硼酸和二取代的丙二腈，可提供多种β-乙腈。该产品可以进一步衍生为有价值的手性α，通过加成反应成相应的α二取代的β氨基腈ñ -叔-butanesulfinyl亚胺。
• Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation
  作者：Kelly E. Kim、Jiaming Li、Robert H. Grubbs、Brian M. Stoltz

  DOI：10.1021/jacs.6b08788

  日期：2016.10.12

  functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups including esters, nitriles, silyl ethers, vinylogous esters, ketones, lactones, and β-ketoesters are tolerated under the reaction conditions

  报道了一种空间位阻末端烯烃功能化的新策略。在烯丙基或同烯丙基位置带有季碳的烯烃很容易被钯/铜/亚硝酸盐催化氧化成相应的醛。在反应条件下可以耐受多种官能团，包括酯、腈、甲硅烷基醚、乙烯基酯、酮、内酯和 β-酮酯。粗醛产物可以进一步转化，使受阻末端烯烃直接转化为各种其他合成有用的官能团，导致正式的反马尔科夫尼科夫加氢胺化等转化。
• 1,4-Dicarbofunctionalization of 4-Fluoroaryl Grignard and Lithium Reagents with Disubstituted Malononitriles
  作者：Christian A. Malapit、Irungu K. Luvaga、Jonathan T. Reeves、Ivan Volchkov、Carl A. Busacca、Amy R. Howell、Chris H. Senanayake

  DOI：10.1021/acs.joc.7b00567

  日期：2017.5.5

  efficient one-pot 1,4-dicarbofunctionalization of 4-fluoroaryl Grignard or lithium reagents with 2,2-disubstituted malononitriles is described. The reaction proceeds by sequential transnitrilation and SNAr reactions. Commercial Grignard solutions, Grignard reagents prepared in situ by halogen/magnesium exchange with i-PrMgCl, or aryllithium reagents prepared in situ by bromine/lithium exchange with n-BuLi

  描述了用2，2-二取代的丙二烯对4-氟芳基格氏试剂或锂试剂的有效的一锅法1，4-二糖官能化。该反应通过顺序transnitrilation和S前进Ñ的Ar反应。市售的格氏溶液，通过与i- PrMgCl进行卤素/镁交换原位制备的格氏试剂，或通过与正丁基锂交换溴/锂原位制备的芳基锂试剂与反应条件兼容。而且，可以容纳各种结构的2，2-二取代的丙二腈。该反应提供了一种独特的方法，以串联，一锅法进行活化的芳烃的1,4-二糖官能化。
• Realization of the synthesis of α,α-disubstituted carbamylacetates and cyanoacetates by either enzymatic or chemical functional group transformation, depending upon the substrate specificity of Rhodococcus amidase
  作者：Masahiro Yokoyama、Mieko Kashiwagi、Masakazu Iwasaki、Ken-ichi Fuhshuku、Hiromichi Ohta、Takeshi Sugai

  DOI：10.1016/j.tetasy.2004.04.047

  日期：2004.9

  Substrate specificity and enantioselectivity of nitrile hydratase and amidase from R. rhodochrous IFO 15564 has been studied by applying a series of alpha,alpha-disubstituted malononitriles and related substrates. The amidase preferentially hydrolyzed the pro-(R) carbamyl group (amide) of the prochiral diamides, an intermediate resulting from the action of nitrile hydratase in a nonenantiotopic group-selective manner. The introduction of a fluorine atom at the alpha-position caused an inhibitory effect on amidase. By a combination of this microbial transformation and the subsequent Hofmann rearrangement, an important precursor of (S)methyldopa with 98.4% ee has been prepared. For the enzymatically poor substrate, the action on HO3SONO-H2O on the carbamyl group was effective, leaving the cyano group intact. This conversion is demonstrated as the key step for the expeditious preparation of (+/-)-alpha-cyano-alpha-fluoro-alpha-phenylacetic acid (CFPA) from diethyl alpha-fluoro-alpha-phenylmalonate. (C) 2004 Elsevier Ltd. All rights reserved.