2-pyridyl N,N-diisopropylcarbamate | 1225288-38-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-pyridyl N,N-diisopropylcarbamate
• 英文别名: pyridin-2-yl diisopropylcarbamate
• CAS: 1225288-38-9
• 化学式: C₁₂H₁₈N₂O₂
• 分子量: 222.287
• InChiKey: OPBZISSXZXYQNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  42.43
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-pyridyl N,N-diisopropylcarbamate 在 四甲基乙二胺 、 仲丁基锂 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以60%的产率得到N,N-diisopropyl-3-iodo-2-pyridyl O-carbamate
  参考文献：
  名称：

  Combined Directed ortho Metalation−Halogen Dance (HD) Synthetic Strategies. HD−Anionic ortho Fries Rearrangement and Double HD Sequences

  摘要：

  A general and efficient directed ortho metalation (DoM)-halogen dance (HD)-electrophile quench sequence for the synthesis of trisubstituted pyridyl O-carbamates is described. A second HD sequence furnishes highly functionalized tetrasubstituted pyridines. Furthermore, a hitherto unobserved double HD rearrangement is reported. Under similar LDA conditions, aromatic O-carbamates with OMe, Cl, and F substituents (4a-c) undergo either a HD-electrophile quench sequence, 4a-c -> 18-20, or a HD-anionic ortho Fries rearrangement, 4a-c -> 6a-c, respectively.

  DOI：

  10.1021/ol100493v
• 作为产物：
  描述：

  2-羟基吡啶 、 二异丙基甲胺酰氯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 0.5h， 以67%的产率得到2-pyridyl N,N-diisopropylcarbamate
  参考文献：
  名称：

  Combined Directed ortho Metalation−Halogen Dance (HD) Synthetic Strategies. HD−Anionic ortho Fries Rearrangement and Double HD Sequences

  摘要：

  A general and efficient directed ortho metalation (DoM)-halogen dance (HD)-electrophile quench sequence for the synthesis of trisubstituted pyridyl O-carbamates is described. A second HD sequence furnishes highly functionalized tetrasubstituted pyridines. Furthermore, a hitherto unobserved double HD rearrangement is reported. Under similar LDA conditions, aromatic O-carbamates with OMe, Cl, and F substituents (4a-c) undergo either a HD-electrophile quench sequence, 4a-c -> 18-20, or a HD-anionic ortho Fries rearrangement, 4a-c -> 6a-c, respectively.

  DOI：

  10.1021/ol100493v

文献信息

• Rhodium-catalyzed cross-coupling of aryl carbamates with arylboron reagents
  作者：Keisuke Nakamura、Kosuke Yasui、Mamoru Tobisu、Naoto Chatani

  DOI：10.1016/j.tet.2015.02.088

  日期：2015.7

  A new method has been developed for the rhodium-catalyzed cross-coupling of aryl carbamates with organoboron reagents. The use of an NHC ligand bearing a 2-adamantyl group, i.e., I(2-Ad), is essential to the success of the reaction. The reaction involves the rhodium-mediated activation of the relatively inert C(aryl)-O bond of aryl carbamates.

  已经开发出一种新方法，用于铑催化的氨基甲酸芳基酯与有机硼试剂的交叉偶联。使用带有2-金刚烷基，即I（2-Ad）的NHC配体对于反应成功是必不可少的。该反应涉及铑介导的氨基甲酸芳基酯的相对惰性的C（芳基）-O键的活化。
• Functionalization of a Pyridine Framework through Intramolecular Reissert-Henze Reaction of<i>N</i>-(Carbamoyloxy)pyridinium Salts and Unexpected Insertion of Ethereal Solvents
  作者：Haruyasu Asahara、Asuka Kataoka、Shotaro Hirao、Nagatoshi Nishiwaki

  DOI：10.1002/ejoc.201500443

  日期：2015.6

  new intramolecular transformation of an acyloxy group from N-carbamoyloxypyridinium salts (Reissert–Henze-type reaction) as the key step. Addition of a silver salt effectively accelerates the intramolecular attack of the carbonyl oxygen at the 2-position of the pyridine ring. Additionally, a new rearrangement of the acyloxy group, combined with insertion of an ethereal solvent to give pyridine derivatives

  报道了合成 2-吡啶基氨基甲酸酯的新策略。该策略利用来自 N-氨基甲酰氧基吡啶鎓盐（Reissert-Henze 型反应）的酰氧基的新分子内转化作为关键步骤。添加银盐可有效加速吡啶环 2 位羰基氧的分子内攻击。此外，还报道了酰氧基的新重排，结合醚溶剂的插入，得到具有配位链的吡啶衍生物。