(2S,3S)-methyl 3-methyl-2-(pyridine-2-sulfonamido)pentanoate | 1423218-69-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3S)-methyl 3-methyl-2-(pyridine-2-sulfonamido)pentanoate
• 英文别名: (2S,3S)-mehyl 3-mehyl-2-(pyridine-2-sulfonamido)pentanoate；methyl (pyridin-2-ylsulfonyl)-L-isoleucinate
• CAS: 1423218-69-2
• 化学式: C₁₂H₁₈N₂O₄S
• 分子量: 286.352
• InChiKey: BTOMBDPLYDBZRP-ONGXEEELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.95
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  85.36
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S,3S)-methyl 3-methyl-2-(pyridine-2-sulfonamido)pentanoate 在 silver(I) acetate 、 palladium diacetate 、 对苯醌 作用下， 以 1,4-二氧六环 为溶剂， 反应 22.0h， 生成 (3S,4R)-mehyl 4-ethyl-8-mehyl-1-oxo-2-(pyridin-2-ylsulfonyl)-2,3,4,5-tetrahydro-1H-benzo[c]azepine-3-carboxylate
  参考文献：
  名称：

  Access to Benzazepinones by Pd-Catalyzed Remote C–H Carbonylation of γ-Arylpropylamine Derivatives

  摘要：

  A general method for the construction of seven-membered rings through Pd-catalyzed C(sp(2))-H carbonylation at the remote epsilon-position of gamma-arylpropylamine derivatives, including chiral alpha-amino acids, has been developed using Mo(CO)(6) as the CO source, furnishing richly functionalized benzo[c]azepin-1-one derivatives. The readily removable N-SO2Py protecting/directing group provides high levels of chemo-, regio- and diastereoselectivity. Furthermore, this method is amenable to the postsynthetic modification of complex molecules such as small peptides.

  DOI：

  10.1021/acs.orglett.9b01523
• 作为产物：
  描述：

  2-巯基吡啶 在 盐酸 、 sodium chlorite 、 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 生成 (2S,3S)-methyl 3-methyl-2-(pyridine-2-sulfonamido)pentanoate
  参考文献：
  名称：

  NaClO2介导的吡啶-2-磺酰氯的制备及手性磺酰胺的合成

  摘要：

  开发了一种以水为溶剂，通过 NaClO2 介导的氮杂芳烃硫醇氧化氯化制备氮杂芳烃磺酰氯的简单方法。通过简单的提取和浓缩，容易纯化得到高产率的产品。氮杂芳烃磺酰氯易于与手性胺缩合得到手性磺酰胺。图形概要

  DOI：

  10.1080/17415993.2020.1775834

文献信息

• Total Synthesis of Hibispeptin A via Pd-Catalyzed C(sp³)–H Arylation with Sterically Hindered Aryl Iodides
  作者：Gang He、Shu-Yu Zhang、William A. Nack、Ryan Pearson、Javon Rabb-Lynch、Gong Chen

  DOI：10.1021/ol503347d

  日期：2014.12.19

  To access the key Ile-Hpa pseudodipeptide motif in hibispeptins, a series of bidentate carboxamide-based auxiliary groups have been explored to facilitate the palladium-catalyzed arylation of unactivated γ-C(sp3)–H bonds of Ile precursor with aryl iodides. A new pyridylmethylamine-based auxiliary group PR is introduced, which permits the use of more sterically hindered ortho-substituted aryl iodide

  为了获得木抑肽素中关键的Ile-Hpa假二肽基序，已研究了一系列基于二齿羧酰胺的辅助基团，以促进钯活化的Ile前体与芳基碘化物的未活化γ-C（sp 3）-H键的芳基化。引入了新的基于吡啶基甲胺的辅助基团PR，该基团允许使用空间更受阻的邻位取代的芳基碘化物底物，并且可以在温和条件下除去。Pd催化的PR定向的γ-C（sp 3）–H芳基化反应实现了抑制肽素A的第一个全合成。
• Palladium-catalyzed N-(2-pyridyl)sulfonyl-directed C(sp³)–H γ-arylation of amino acid derivatives
  作者：Nuria Rodríguez、Jose A. Romero-Revilla、M. Ángeles Fernández-Ibáñez、Juan C. Carretero

  DOI：10.1039/c2sc21162a

  日期：——

  The direct Pd-catalyzed γ-arylation of amino acid esters bearing a removable N-(2-pyridyl)sulfonyl directing group is described. A variety of N-(2-pyridyl)sulfonamide amino acid derivatives, including α-quaternary amino acid and β-amino acid substrates, react with iodoarenes in the presence of Pd(OAc)2 to provide γ-arylated products in synthetically useful yields. An unprecedented remote C(sp3)–H arylation of dipeptides is presented, illustrating the compatibility of the method with the presence of the peptidic bond. The process occurs without racemization at the Cα center and the auxiliary controlling group can be easily installed and removed in the amino acid backbone. A bimetallic PdII γ-metalated complex has been isolated and characterized showing the key role exerted by the (2-pyridyl)sulfonyl unit.

  描述了一种直接的Pd催化γ-芳基化反应，适用于带有可去除的N-(2-吡啶基)磺酰指向基团的氨基酸酯。多种N-(2-吡啶基)磺酰胺氨基酸衍生物，包括α-四取代氨基酸和β-氨基酸底物，在Pd(OAc)2的存在下与碘芳烃反应，生成合成有用产率的γ-芳基化产品。提出了一种前所未有的远程C(sp3)–H芳基化反应，用于二肽，展示了该方法与肽键存在的兼容性。该过程在Cα中心不发生外消旋化，并且辅助控制基团可以很方便地在氨基酸骨架中安装和去除。分离并表征出一种双金属PdII γ-金属化复合物，显示了(2-吡啶基)磺酰单元所发挥的关键作用。
• Palladium‐Catalyzed PIDA‐Mediated δ‐C(sp ³ )−H Acetoxylation of Amino Acid Derivatives: Overriding Competitive Intramolecular Amination
  作者：Mario Martínez‐Mingo、Andrés García‐Viada、Daniel Sowa Prendes、Inés Alonso、Nuria Rodríguez、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1002/anie.202209865

  日期：2022.11.21

  Selective δ-C(sp3)−H acetoxylation of amino acid derivatives has been achieved by using palladium-catalysis and PhI(OAc)2 (PIDA) as terminal oxidant and acetoxy source. The N-SO2Py protecting/directing group plays a key role in enabling control of chemoselectivity (intermolecular C−O over intramolecular C−N bond formation) and regioselectivity (favoring δ-CH3 over γ-CH2 activation).

  通过使用钯催化和PhI(OAc) 2 (PIDA)作为末端氧化剂和乙酰氧基源，实现了氨基酸衍生物的选择性δ-C(sp 3 )−H乙酰氧基化。 N -SO 2 Py 保护/导向基团在控制化学选择性（分子间 CO 对分子内 CN 键形成）和区域选择性（有利于 δ-CH 3而不是 γ-CH 2活化）方面发挥着关键作用。