(2S*,3S*)-mehyl 3-(4-mehylbenzyl)-2-(pyridine-2-sulfonamido)pentanoate

• 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*)-mehyl 3-(4-mehylbenzyl)-2-(pyridine-2-sulfonamido)pentanoate
• 英文别名: methyl (2S,3S)-3-[(4-methylphenyl)methyl]-2-(pyridin-2-ylsulfonylamino)pentanoate
• 化学式: C₁₉H₂₄N₂O₄S
• 分子量: 376.477
• InChiKey: POILVQZHWULTGC-WMZOPIPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  93.7
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S*,3S*)-mehyl 3-(4-mehylbenzyl)-2-(pyridine-2-sulfonamido)pentanoate 在 silver(I) acetate 、 对苯醌 作用下， 以 1,4-二氧六环 为溶剂， 反应 18.0h， 生成 (3S*,4S*)-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：

  吡啶-2-磺酰氯 在 吡啶 、 silver(I) acetate 、 palladium diacetate 作用下， 以 乙腈 为溶剂， 反应 22.0h， 生成 (2S*,3S*)-mehyl 3-(4-mehylbenzyl)-2-(pyridine-2-sulfonamido)pentanoate
  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

文献信息

• Overcoming the Necessity of γ-Substitution in δ-C(sp³)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids
  作者：Mario Martínez-Mingo、Andrés García-Viada、Inés Alonso、Nuria Rodríguez、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1021/acscatal.1c00250

  日期：2021.5.7

  catalytic C(sp3)–H arylation at the remote δ-position via challenging six-membered ring cyclometalation, the requirement of blocking the more reactive γ-position represents a restricting limitation. The use of the removable N-(2-pyridyl)sulfonyl directing group provides a viable solution to this challenge, expanding the scope of the Pd-catalyzed δ-C–H arylation of α-amino acid and amine derivatives with

  尽管通过具有挑战性的六元环金属环化在远端δ位出现了催化性C（sp 3）-H芳基化反应，但需要封闭更具反应性的γ位仍然是一个限制性限制。可移动的N-（2-吡啶基）磺酰基导向基团的使用为解决这一难题提供了可行的解决方案，扩大了Pd催化的α-氨基酸和胺衍生物与（杂）芳基的δ-CH芳基化反应的范围。碘化物。该方法与任一反应伙伴处的复杂多功能结构兼容。实验和密度泛函理论研究提供了有关控制位点选择性的潜在因素的见解。
• 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。
• Mechanistic understanding enables chemoselective sp³ over sp² C–H activation in Pd-catalyzed carbonylative cyclization of amino acids
  作者：Mario Martínez-Mingo、Inés Alonso、Nuria Rodríguez、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1039/d0cy02328k

  日期：——

  chemoselectivity in competing C(sp2)–H and C(sp3)–H activation pathways in the palladium-catalyzed carbonylative cyclization of γ-arylated valine type derivatives, gained by experimental observations and DFT studies, have been leveraged to reverse the remarkable selectivity of Pd for arene C(sp2)–H activation over C(sp3)–H cleavage. These studies suggest that ε-C(sp2)–H bond cleavage is significantly faster and more

  通过实验观察和DFT研究获得了在钯催化的γ-芳基化缬氨酸类型衍生物的羰基环化中竞争性C（sp 2）–H和C（sp 3）–H竞争途径中控制化学选择性的因素的机理见解，已被利用来扭转Pd对芳烃C（sp 2）–H活化的显着选择性，而不是C（sp 3）–H裂解。这些研究表明，与γ-C（sp 3）-H键激活相比，ε-C（sp 2）-H键的裂解明显更快，并且更可逆，而随后的AcOH / CO交换和C（sp 3的CO插入））-Paladacycle产生了更稳定的中间体，从中不可逆地反应。通过发挥反应条件以使热力学优于动力学控制，已经实现了对化学选择性的控制。解决Pd催化下C–H官能化的这一基本局限性，使得能够从同一起始底物中获得不同的杂环骨架（即γ-内酰胺而不是苯并ze庚酮骨架）。