(+)-(R)-N-(1-cyano-2-phenyl-ethyl)-acetamide | 181376-74-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(R)-N-(1-cyano-2-phenyl-ethyl)-acetamide
• 英文别名: N-(1-cyano-2-phenylethyl)acetamide；N-acetyl-(R)-2-amino-3-phenylpropionitrile；N-[(1R)-1-cyano-2-phenylethyl]acetamide
• CAS: 181376-74-9
• 化学式: C₁₁H₁₂N₂O
• 分子量: 188.229
• InChiKey: QVXLUXTYHOISLH-LLVKDONJSA-N

物化性质

• 沸点：
  434.5±38.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  52.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-己炔 、 (+)-(R)-N-(1-cyano-2-phenyl-ethyl)-acetamide 在 decamethylrhenocene 作用下， 以 甲苯 为溶剂， 以87%的产率得到(+)-(R)-N-[2-phenyl-1-(3,4,5,6-tetraethyl-pyridin-2-yl)-ethyl]-acetamide
  参考文献：
  名称：

  手性腈向吡啶衍生物的简便无外消旋转化。

  摘要：

  本文所述的结果证明了Co（I）催化的光化学[2 + 2 + 2]环共三聚反应的温和反应条件如何适合于从手性腈开始制备包含未取代和多取代的2-吡啶基部分的手性化合物，而没有任何可检测到的损失对映体纯度。这进一步增加了该特定反应已经非常广泛的合成范围。

  DOI：

  10.1021/jo030206t
• 作为产物：
  描述：

  2-cyano-3-phenylaziridine 在 palladium on activated charcoal 氢气 作用下， 生成 (+)-(R)-N-(1-cyano-2-phenyl-ethyl)-acetamide
  参考文献：
  名称：

  Preparation of N–H azirdines in high enantiomeric excess by in situ aziridine–azirine–aziridine interconversion

  摘要：

  Aziridine 6 is produced highly diastereoselectively by treatment of enantiopure 3-acetoxyaminoquinazolinone 4 (Q*NHOAc) with beta-trimethylsilylstyrene: desilylative elimination of Q* and in situ addition of cyanide to the intermediate azirine gives the NH-aziridine 8 of 83% ee.

  DOI：

  10.1039/cc9960000789

文献信息

• Reagent-controlled diastereoselectivity in aziridination of alkenes by chiral 3-acetoxyamino-3,4-dihydroquinazolin-4-ones: 1′-(t-butyldimethylsilyloxy)ethyl as the chiral 2-substituent on the quinazolinone
  作者：Robert S. Atkinson、Michael P. Coogan、Ian S.T. Lochrie

  DOI：10.1016/0040-4039(96)01055-6

  日期：1996.7

  Conformational preferences within the tBuMe2SiOCH(Me)CN unit in 3-acetoxyaminoquinazolinone 3 lead to well defined site preferences for H, Me and OSiMe2tBu in the transition state for, and hence high diastereoselectivity in, its reaction with β-trimethylsilylstyrene 4 to give aziridine 5.

  3-乙酰氧基氨基喹唑啉酮3中的t BuMe 2 SiOCH （Me）CN单元内的构象偏爱导致H，Me和OSiMe 2 t Bu在过渡态的确定位置偏爱，因此与它的反应具有非对映选择性。 β-三甲基甲硅烷基苯乙烯4得到氮丙啶5。
• Process for the preparation of enantiomerically enriched compounds
  申请人：DSM IP Assets B.V.

  公开号：EP1352894A1

  公开（公告）日：2003-10-15

  1. Process for the preparation of enantiomerically enriched amino aldehydes and amino alcohols, wherein a corresponding enantiomerically enriched amino nitrile is subjected to hydrogenation in the presence of hydrogen, a hydrogenation catalyst, preferably a Pd-catalyst and a mineral acid. For the preparation of an amino aldehyde hydrogen preferably is present at a hydrogen-pressure between 0.1 and 2 MPa, in particular between 0.5 and 1 MPa. The amino aldehyde preferably is isolated in the form of a chemically and configurationally stable derivative. For the preparation of an amino alcohol, preferably at least during part of the hydrogenation hydrogen is present at a hydrogen-pressure between 2 and 10 MPa, in particular between 4 and 6 MPa. In a preferred embodiment the hydrogen-pressure initially is between 0,5 and 2 MPa and subsequently, after most of the nitrile starting material is converted, the hydrogen pressure is increased to a value between 2 and 10 MPa. The enantiomerically enriched nitrile starting material may a.o. be prepared by enzymatic resolution, classical resolution, resolution via preferential crystallization, diastereomeric synthesis, catalytic asymmetric synthesis or dehydratation of amino acid amides.

  制备对映富集的氨基醛和氨基醇的过程，其中对应的对映富集的氨基腈在氢气、氢化催化剂（最好是Pd催化剂）和矿酸存在下进行加氢。用于制备氨基醛时，最好在氢压力在0.1至2兆帕之间，特别是在0.5至1兆帕之间。氨基醛最好以化学和构型稳定的衍生物形式分离。用于制备氨基醇时，最好在加氢的部分时间内氢气的压力在2至10兆帕之间，特别是在4至6兆帕之间。在一种首选实施方式中，氢气压力最初在0.5至2兆帕之间，随后，在大部分腈起始物质被转化后，氢气压力增加到2至10兆帕之间的值。对映富集的腈起始物质可以通过酶解、经典分离、通过优先结晶分离、对映异构合成、催化不对称合成或氨基酸酰胺的脱水制备等方法制备。
• Acceptor-Controlled Transfer Dehydration of Amides to Nitriles
  作者：Hiroyuki Okabe、Asuka Naraoka、Takahiro Isogawa、Shunsuke Oishi、Hiroshi Naka

  DOI：10.1021/acs.orglett.9b01657

  日期：2019.6.21

  dehydration of primary amides to nitriles efficiently proceeds under mild, aqueous conditions via the use of dichloroacetonitrile as a water acceptor. A key to the design of this transfer dehydration catalysis is the identification of an efficient water acceptor, dichloroacetonitrile, that preferentially reacts with amides over other polar functional groups with the aid of the Pd catalyst and makes the desired

  通过使用二氯乙腈作为水受体，在温和的水性条件下钯催化的伯酰胺脱水有效地进行为腈。设计该转移脱水催化的关键是确定一种有效的水受体二氯乙腈，该水受体在Pd催化剂的帮助下优先于酰胺而不是其他极性官能团反应，并使所需的反应体系趋于能动，从而驱动脱水。
• Rhodium-catalyzed enantioselective hydrogenation of α-amino acrylonitriles: an efficient approach to synthesizing chiral α-amino nitriles
  作者：Xiuxiu Li、Cai You、Yusheng Yang、Fangyuan Wang、Shuailong Li、Hui Lv、Xumu Zhang

  DOI：10.1039/c6cc09662j

  日期：——

  An efficient asymmetric hydrogenation of [small alpha]-amino acrylonitriles has been achieved, affording chiral [small alpha]-amino nitriles in excellent yields and enantioselectivities regardless of the cis-trans configuration of [small alpha]-amino acrylonitriles.

  已经实现了对小α-氨基丙烯腈的有效不对称氢化，无论其为小α-氨基丙烯腈的顺式-反式构型，都以优异的收率和对映选择性提供了手性的小α-氨基腈。
• Desilylative elimination of the quinazolinone ring from 1-(4-oxoquinazolin-3-yl)-2-silylaziridines; preparation of an N–H aziridine in high enantiomeric excess by in situ nucleophilic addition to the derived azirine
  作者：Robert S. Atkinson、Michael P. Coogan、Ian S. T. Lochrie

  DOI：10.1039/a606092g

  日期：——

  Aziridination of vinylsilanes PhCHCHSiR3 (R = Me, Et, Ph) with enantiopure 3-acetoxyaminoquinazolinone 11 gives the corresponding aziridines 12 [diastereoisomer ratio (dr) 10∶1], 18 (dr 13∶1) and 20 (dr 2∶1). Desilylative elimination of the quinazolinone from these aziridines by caesium fluoride in the presence of cyanide gives aziridine 14 by cyanide addition to the 3-unsubstituted azirine 13, produced in situ. Acylation of aziridine 14 with (S)-acetoxypropionyl chloride gives N-acylaziridine 16; the good correlation between the diastereoisomer ratios of aziridines 12, 18 and 20 and those of the N-acylaziridine 16 produced in each case suggests that intermediate azirine 13 is configurationally stable.

  乙烯基硅烷的氮丙啶化 PhCHCHSiR3 (R = Me, Et, Ph) 与 对映体纯 3-乙酰氧基氨基喹唑啉酮 11 给出 相应的氮丙啶 12 [非对映异构体比例 (dr) 10-1]、18（13-1 博士）和 20（2-1 博士）。 从这些物质中脱甲硅烷基消除喹唑啉酮 在氰化物存在下与氟化铯反应生成氮丙啶 氮丙啶 14 通过氰化物加成到 3-未取代的氮丙啶上 13、原地制作。氮丙啶 14 的酰化 (S)-乙酰氧基丙酰氯得到 N-酰基氮丙啶16；之间的良好相关性 氮丙啶 12、18 和 20 的非对映异构体比例 每种情况下产生的 N-酰基氮丙啶 16 表明 中间体氮丙啶 13 在构型上是 稳定的。