1-(2,2-dimethylpropanoyl)cyclohexanecarbonitrile

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(2,2-dimethylpropanoyl)cyclohexanecarbonitrile
• 英文别名: 1-pivaloylcyclohexanecarbonitrile；1-(2,2-Dimethylpropanoyl)cyclohexane-1-carbonitrile
• 化学式: C₁₂H₁₉NO
• mdl: MFCD09030935
• 分子量: 193.289
• InChiKey: HEHVCFDXJQRAMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.833
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  环己甲腈 在 吡啶 、 五氯化磷 、 异丙基溴化镁 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 18.0h， 生成 1-(2,2-dimethylpropanoyl)cyclohexanecarbonitrile
  参考文献：
  名称：

  金属化腈：α-卤代腈的有机锂，-镁和-铜交换

  摘要：

  α-卤代腈与烷基锂，有机镁和二甲基cup酸锂试剂反应生成活性的金属化腈。与烷基锂和格氏试剂的快速卤素金属交换可在存在醛的反应性羰基亲电试剂存在下进行选择性交换，从而提供了高产率的烷基化方案。锂化和氧化镁腈通过S N 2置换与炔丙基溴反应，而有机铜腈通过S N 2'置换反应，与C-金属化腈的形成相关。

  DOI：

  10.1021/jo047877r

文献信息

• Metalated Nitriles:  Halogen−Metal Exchange with α-Halonitriles
  作者：Fraser F. Fleming、Zhiyu Zhang、Paul Knochel

  DOI：10.1021/ol036202s

  日期：2004.2.1

  [reaction: see text] Alpha-halonitriles react with organometallic reagents in a facile halogen-metal exchange. The halogen-metal exchange is extremely fast with Grignard and alkyllithium reagents, generating metalated nitriles in situ with aldehyde, ketone, acid chloride, and acyl cyanide electrophiles. Sequential halogen-metal exchange and methylation of conformationally constrained nitriles is highly

  [反应：见正文]α-卤代腈与有机金属试剂反应，易于进行卤素-金属交换。用格氏试剂和烷基锂试剂进行卤素金属交换非常快，可与醛，酮，酰氯和酰基氰亲电试剂原位生成金属化的腈。构象受限的腈的顺序卤素金属交换和甲基化具有高度立体选择性，并且与C-镁化的腈的保持性烷基化相一致。
• Nitrile Alkylations through Sulfinyl-Metal Exchange
  作者：Dinesh Nath、Fraser F. Fleming

  DOI：10.1002/anie.201105630

  日期：2011.12.2

  Triple alkylation: Phenylsulfinyl‐ and phenylthioacetonitrile can function as trianion equivalents of acetonitrile by sequential alkylation and sulfinyl–metal exchange (see scheme; mCPBA=meta‐chloroperoxybenzoic acid). The metalated nitriles alkylate a range of electrophiles to obtain nitriles with quaternary centers. The sulfinyl–metal exchange proceeds under very mild conditions and has a high functional‐group

  三重烷基化：通过顺序烷基化和亚磺酰基-金属交换，苯亚磺酰基和苯硫基乙腈可以作为乙腈的三价阴离子（见方案；m CPBA =间-氯过氧苯甲酸）。金属化的腈使一系列亲电试剂烷基化以获得具有季中心的腈。亚磺酰基-金属的交换在非常温和的条件下进行，并且具有很高的官能团耐受性。
• Sulfinylnitriles: Sulfinyl-Metal Exchange-Alkylation Strategies
  作者：Dinesh Nath、Fraser F. Fleming

  DOI：10.1002/chem.201203174

  日期：2013.2.4

  organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl–metal exchange to afford N‐ or C‐metalated nitriles. Sulfinyl–magnesium exchange–alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α‐Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and

  添加有机锂，格氏试剂，或锌酸盐到sulfinylnitriles触发器一个浅显亚磺酰基-金属交换，得到N -或C -金属化的腈。亚磺酰基-镁交换-烷基化有效地建立了四级和三级中心，即使在具有高酸性次甲基质子的叔亚磺酰基腈的情况下也是如此。α-亚磺酰基烯腈提供适度的亲核性镁化腈，通过转化为相应的镁酸酯可以显着提高反应性。亚磺酰基-金属交换非常快，可与季，叔和乙烯基α-亚磺酰基腈有效地进行交换，并且在腈烷基化反应中表现出出色的官能团耐受性。
• Palladium-Catalyzed α,β-Dehydrogenation of Esters and Nitriles
  作者：Yifeng Chen、Justin P. Romaire、Timothy R. Newhouse

  DOI：10.1021/jacs.5b02243

  日期：2015.5.13

  A highly practical and general palladium-catalyzed methodology for the alpha,beta-dehydrogenation of esters and nitriles is repotted. Generation of a zinc enolate or (cyanoalkyl)zinc species followed by the addition of an allyl oxidant and a palladium catalyst results in synthetically useful yields of alpha,beta-unsaturated esters, lactones, and nitriles. Preliminary mechanistic investigations are consistent with reversible beta-hydride elimination and turnover-limiting, propene-forming reductive elimination.
• PYRROLIDINYL SULFONE DERIVATIVES AND THEIR USE AS ROR GAMMA MODULATORS
  申请人：Bristol-Myers Squibb Company

  公开号：US20160326108A1

  公开（公告）日：2016-11-10

  Described are RORγ modulators of the formula (I), or stereoisomers, tautomers, pharmaceutically acceptable salts, solvates, or prodrugs thereof, wherein all substituents are defined herein. Also provided are pharmaceutical compositions comprising the same. Such compounds and compositions are useful in methods for modulating RORγ activity in a cell and methods for treating a subject suffering from a disease or disorder in which the subject would therapeutically benefit from modulation of RORγ activity, for example, autoimmune and/or inflammatory disorders.