3-bromo-2-phenyl-2-trimethylsilyloxy-propionitrile

• 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: 3-bromo-2-phenyl-2-trimethylsilyloxy-propionitrile
• 英文别名: 3-Bromo-2-phenyl-2-trimethylsilyloxypropanenitrile
• 化学式: C₁₂H₁₆BrNOSi
• 分子量: 298.255
• InChiKey: SKYLXBZYFGCWHG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三甲基氰硅烷 、 2-溴苯乙酮 在 C₁₆H₂₆N₂Sb⁽¹⁺⁾*F₆Sb^(1-) 作用下， 以 neat (no solvent) 为溶剂， 以97%的产率得到3-bromo-2-phenyl-2-trimethylsilyloxy-propionitrile
  参考文献：
  名称：

  无供体的锑阳离子作为一种有效的氰基化催化剂

  摘要：

  已经描述了新型锶阳离子的合成及其在羰基化合物的氰基化中的催化应用。用 1 equiv处理氯锑 L 1 SbCl [L 1 = 1,2-C 6 H 4 {N(CH 2 t Bu)} 2 ] (2)。AgOTf 和 A​​gSbF 6分别导致无供体 L 1 SbOTf ( 3 ) 和 [L 1 Sb] + [SbF 6 ] - ( 4 ) 的形成。在这三种化合物中，4种对醛和酮的氰基化反应表现出优异的催化活性。

  DOI：

  10.1039/d2cc03158b

文献信息

• Catalytic Activation of 1-Cyano-3,3-dimethyl-3-(1<i>H</i>)-1,2-benziodoxole with B(C₆F₅)₃ Enabling the Electrophilic Cyanation of Silyl Enol Ethers
  作者：Takaya Nagata、Hiroki Matsubara、Kensuke Kiyokawa、Satoshi Minakata

  DOI：10.1021/acs.orglett.7b02313

  日期：2017.9.1

  cyano group, 1-cyano-3,3-dimethyl-3-(1H)-1,2-benziodoxole (CDBX), with B(C6F5)3, to achieve the catalytic electrophilic cyanation of silyl enol ethers is presented. Mechanistic studies indicate that CDBX is activated through coordination of its cyano group to B(C6F5)3, thus enabling the electrophilic cyanation reaction to occur.

  含有可转移氰基，1-氰基-3,3-二甲基-3-（1 H）-1,2-苯并恶唑（CDBX）和B（C 6 F 5）3的高价碘试剂的路易斯酸性活化提出了实现甲硅烷基烯醇醚的催化亲电子氰化的方法。机理研究表明，CDBX通过其氰基与B（C 6 F 5）3配位而被激活，从而使亲电氰化反应发生。
• A Convenient Catalytic Procedure for the Addition of Trimethylsilyl Cyanide to Functionalised Ketones, Mediated by InBr3 − Insight into the Reaction Mechanism
  作者：Marco Bandini、Pier Giorgio Cozzi、Andrea Garelli、Paolo Melchiorre、Achille Umani-Ronchi

  DOI：10.1002/1099-0690(200210)2002:19<3243::aid-ejoc3243>3.0.co;2-e

  日期：2002.10

  This paper describes a useful and practical methodology for the addition of trimethylsilyl cyanide (TMSCN) to a large variety of functionalised and unfunctionalised ketones in the presence of catalytic amounts of anhydrous InBr3. The optimum procedure involves low catalyst loading (1 mol %) and appears general in scope and applicability for aromatic and aliphatic ketones. The desired cyanohydrins were

  本文描述了一种有用且实用的方法，用于在催化量的无水 InBr3 存在下将三甲基氰化硅烷 (TMSCN) 添加到多种官能化和未官能化的酮中。最佳程序涉及低催化剂负载（1 mol %），并且在芳香族和脂肪族酮的范围和适用性上似乎很普遍。所需的氰醇通常以 O-甲硅烷基醚的形式分离，化学产率良好至极好（高达 99%）。动力学和光谱研究表明，催化活性二聚铟物种参与反应机制。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
• Activation of TMSCN by N-Heterocyclic Carbenes for Facile Cyanosilylation of Carbonyl Compounds
  作者：Jinhua J. Song、Fabrice Gallou、Jonathan T. Reeves、Zhulin Tan、Nathan K. Yee、Chris H. Senanayake

  DOI：10.1021/jo052206u

  日期：2006.2.1

  were found to be highly effective organocatalysts in activating TMSCN for facile cyanosilylation of carbonyl compounds. Cyano transfer from TMSCN to aldehydes and ketones proceeds at room temperature in the presence of only 0.01−0.5 mol % of N-heterocyclic carbene (1), leading to a range of trimethylsilylated cyanohydrins in very good to excellent yields. These conditions are extremely mild and simple

  N-杂环卡宾是激活TMSCN进行羰基化合物氰基硅烷化反应的高效有机催化剂。在仅存在0.01-0.5 mol％N-杂环卡宾（1）的情况下，室温下从TMSCN转移到醛和酮的氰基转移，从而导致一系列三甲基甲硅烷基化的氰醇，其收率非常好至极佳。这些条件非常温和和简单，并且可以耐受各种官能团。
• Iodine as novel reagent for the 1,2-addition of trimethylsilyl cyanide to ketones including α,β-unsaturated ketones
  作者：J.S. Yadav、B.V.S. Reddy、M.Sridhar Reddy、A.R. Prasad

  DOI：10.1016/s0040-4039(02)02321-3

  日期：2002.12

  Molecular iodine is found to catalyze efficiently the addition of trimethylsilyl cyanide to a range of simple and functionalized ketones under very mild and convenient conditions to afford the corresponding cyanohydrin trimethylsilyl ethers in excellent yields in a short reaction period with high selectivity. a,P-Unsaturated ketones selectively afford the corresponding 1,2-adducts without the formation of 1,4-adducts under similar reaction conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Indium tribromide: a highly effective catalyst for the addition of trimethylsilyl cyanide to α-hetero-substituted ketones
  作者：Marco Bandini、Pier Giorgio Cozzi、Paolo Melchiorre、Achille Umani-Ronchi

  DOI：10.1016/s0040-4039(01)00368-9

  日期：2001.4

  The catalytic addition of trimethylsilyl cyanide (TMSCN) to a large variety of hetero-substituted ketones promoted by anhydrous InBr3 has been studied. The low catalytic loading (0.1-1 mol%) and the mild experimental conditions required represent the key features of this novel catalytic system. (C) 2001 Elsevier Science Ltd. All rights reserved.