(E)-2-methylcyclohexanone O-methyl oxime

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-2-methylcyclohexanone O-methyl oxime
• 英文别名: 2-Methylcyclohexanone o-methyl oxime；(E)-N-methoxy-2-methylcyclohexan-1-imine
• 化学式: C₈H₁₅NO
• 分子量: 141.213
• InChiKey: RDIZKCYOXFFPNV-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  p-chlorobenzenesulfonyl azide 、 (E)-2-methylcyclohexanone O-methyl oxime 在 bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 silver(I) acetate 、 双三氟甲烷磺酰亚胺银盐 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以85%的产率得到(E)-N-[{2-(methoxyimino)cyclohexyl}methyl]-4-nitrobenzenesulfonamide
  参考文献：
  名称：

  Iridium-Catalyzed Intermolecular Amidation of sp³ C–H Bonds: Late-Stage Functionalization of an Unactivated Methyl Group

  摘要：

  Reported herein is the iridium-catalyzed direct amidation of unactivated sp(3) C-H bonds. With sulfonyl and acyl azides as the amino source, the amidation occurs efficiently under mild conditions over a wide range of unactivated methyl groups with high functional group tolerance. This procedure can be successfully applied for the direct introduction of an amino group into complex compounds and thus can serve as a powerful synthetic tool for late-stage C-H functionalization.

  DOI：

  10.1021/ja501014b
• 作为产物：
  描述：

  甲氧基胺盐酸盐 、 2-甲基环己酮 在 吡啶 作用下， 生成 (E)-2-methylcyclohexanone O-methyl oxime
  参考文献：
  名称：

  Iridium-Catalyzed Intermolecular Amidation of sp³ C–H Bonds: Late-Stage Functionalization of an Unactivated Methyl Group

  摘要：

  Reported herein is the iridium-catalyzed direct amidation of unactivated sp(3) C-H bonds. With sulfonyl and acyl azides as the amino source, the amidation occurs efficiently under mild conditions over a wide range of unactivated methyl groups with high functional group tolerance. This procedure can be successfully applied for the direct introduction of an amino group into complex compounds and thus can serve as a powerful synthetic tool for late-stage C-H functionalization.

  DOI：

  10.1021/ja501014b

文献信息

• Iridium‐Catalyzed β‐Alkynylation of Aliphatic Oximes as Masked Carbonyl Compounds and Alcohols
  作者：Eric Tan、Margherita Zanini、Antonio M. Echavarren

  DOI：10.1002/anie.202002948

  日期：2020.6.22

  An Ir‐catalyzed C(sp3)−H alkynylation of aliphatic ketones, aldehydes, and alcohols was achieved by using the corresponding oxime derivatives and a IrIII catalyst. This general reaction is selective towards primary C(sp3)−H bonds and can be used for the late‐stage C−H alkynylation of complex molecules.

  通过使用相应的肟衍生物和Ir III催化剂可实现Ir催化的脂肪族酮，醛和醇的C（sp 3）-H烷基化反应。该一般反应对主要的C（sp 3）-H键具有选择性，可用于复杂分子的后期C-H炔基化反应。
• Rhodium(III)-Catalyzed Activation of C sp 3H Bonds and Subsequent Intermolecular Amidation at Room Temperature
  作者：Xiaolei Huang、Yan Wang、Jingbo Lan、Jingsong You

  DOI：10.1002/anie.201504507

  日期：2015.8.3

  Disclosed herein is a RhIII‐catalyzed chelation‐assisted activation of unreactive CH bonds, thus enabling an intermolecular amidation to provide a practical and step‐economic route to 2‐(pyridin‐2‐yl)ethanamine derivatives. Substrates with other N‐donor groups are also compatible with the amidation. This protocol proceeds at room temperature, has a relatively broad functional‐group tolerance and high

  本文公开了Rh III催化的非反应性CH键的螯合辅助活化，从而使分子间酰胺化为2-（吡啶-2-基）乙胺衍生物提供了实用而又经济的途径。具有其他N-给体基团的底物也与酰胺化反应相容。该方案在室温下进行，具有相对宽泛的官能团耐受性和高选择性，并证明了铑（III）在促进未反应的CH键官能化方面的潜力。具有的SbF甲rhodacycle 6 -的抗衡离子被确定为一个合理的中间。
• Rhodium(III)‐Catalyzed Amidation of Unactivated C(sp ³ )H Bonds
  作者：He Wang、Guodong Tang、Xingwei Li

  DOI：10.1002/anie.201506323

  日期：2015.10.26

  Nitrogenation by direct functionalization of CH bonds represents an important strategy for constructing CN bonds. Rhodium(III)‐catalyzed direct amidation of unactivated C(sp3)H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp3)H bonds are amidated under rhodium catalysis in high efficiency using 3‐substituted 1,4,2‐dioxazol‐5‐ones as the amide source. The

  通过CH键的直接官能化进行的硝化是构建CN键的重要策略。铑（III）催化的未活化C（sp 3）H键直接酰胺化的现象很少，尤其是在温和的反应条件下。在此，使用3-取代的1,4,2-二恶唑-5-酮类作为酰胺源，在铑催化下高效地酰胺化了大范围的C（sp 3）H键。该协议扩大了铑（III）催化的C（sp 3）H活化化学的范围，适用于天然产物的后期功能化。
• [EN] OXIME COMPOUNDS AS HDL-CHOLESTEROL RAISING AGENTS<br/>[FR] COMPOSÉS D'OXIME EN TANT QU'AGENTS AUGMENTANT LE HDL-CHOLESTÉROL
  申请人：HOFFMANN LA ROCHE

  公开号：WO2012080144A1

  公开（公告）日：2012-06-21

  The present invention relates to compounds of the formula (I) wherein A1 to A3 and R1 to R9 are defined in the description, and to pharmaceutically acceptable salts thereof, their manufacture, pharmaceutical compositions containing them and their use as medicaments for the treatment and/or prophylaxis of diseases which can be treated with HDL-cholesterol raising agents, such as particularly dyslipidemia, atherosclerosis and cardiovascular diseases.

  本发明涉及公式（I）中的化合物，其中A1至A3和R1至R9在描述中有定义，以及其药用盐，其制备方法，含有它们的药物组合物以及它们作为治疗和/或预防可用高密度脂蛋白胆固醇升高剂治疗的疾病的药物的用途，例如特别是脂质代谢异常，动脉粥样硬化和心血管疾病。
• Multicomponent coupling and macrocyclization enabled by Rh(III)-catalyzed dual C–H activation: Macrocyclic oxime inhibitor of influenza H1N1
  作者：Hao Wang、Zhongyu Li、Xiangyang Chen、Jonathan J. Wong、Tongyu Bi、Xiankun Tong、Zhongliang Xu、Mingyue Zhen、Yunhui Wan、Li Tang、Bo Liu、Xinlei Zong、Dandan Xu、Jianping Zuo、Li Yang、Wei Huang、Kendall N. Houk、Weibo Yang

  DOI：10.1016/j.chempr.2022.10.019

  日期：2023.3

  dual C–H activation macrocyclization strategy entailing an in situ-generated directing group. The reaction mode is based on Rh(III)-catalyzed three-component coupling involving cascade C(sp3)–H/C(sp2)–H bond dual activation. The process is facilitated by readily obtainable amidation reagents, namely, aryl-substituted 1,4,2-dioxazol-5-ones, which can be transformed into amide directing groups via a rhodium-nitrene

  在此，我们描述了一种实用的流线型双组分双 C-H 活化大环化策略，需要原位生成的导向基团。反应模式基于 Rh(III) 催化的三组分偶联，涉及级联 C(sp 3 )–H/C(sp 2)–H键双重激活。该过程通过容易获得的酰胺化试剂，即芳基取代的 1,4,2-二恶唑-5-酮，可以通过铑-氮烯中间体转化为酰胺导向基团来促进。DFT 计算表明，C-N 与 C-C 键形成的化学选择性是高度可控的。各种复杂的天然大环化合物、三萜类化合物、生物活性分子和药物的后期 C-H 官能化突出了这种多组分反应的合成效用。此外，所开发的方法能够方便和多样化地合成复杂的大环内酰胺，表型筛选表明通过该策略获得的几种独特的含肟大环内酰胺显示出强大的抗流感 (H1N1) 活性，没有明显的细胞毒性作用。