吡咯并[1,2-a]喹喔啉是一类具有广泛生物活性和刚性结构的含氮杂环化合物，在药物研发（如抗肿瘤、抗糖尿病、抗疟疾等）和材料科学（如有机发光二极管、传感器、有机太阳能电池等）等领域中展现出广泛的应用潜力。然而，因为其主要骨架的传统合成方法通常选择性低、步骤繁多，而且难以精准构建多取代衍生物。因此本文以C-H活化反应为核心，开发一系列绿色、高效的合成方法，成功实现了吡咯并[1,2-a]喹喔啉的芳基化、胺化、硒化、硫化以及烯化等反应。
钯催化的C-H芳基化反应是以醋酸钯为催化剂，与X-Phos配体的协同作用，在甲苯溶剂中，以芳基碘化物实现了在吡咯并[1,2-a]喹喔啉的直接C-H芳基化反应。通过调节底物比例和空间位阻，可选择性合成单芳基化（C1位）或双芳基化（C1和C3位）产物，产率达44%-88%。该反应条件温和，底物适用范围广，兼容给电子和吸电子基团，且可进行克级制备（产率65%）。
钯催化的C-H烯化反应也以醋酸钯为催化剂，和配体L-焦谷氨酸相互作用，与烯丙基酯（如丙烯酸乙酯和金刚烷衍生的酯）在乙酸中进行吡咯并[1,2-a]喹喔啉的C3-H烯基化反应，产率达到81%，同时也实现了与L-薄荷醇衍生物等生物活性分子的偶联，并顺利获得目标产物。
吡咯并[1,2-a]喹喔啉的C-H硒化/硫化反应，是在碘（I2）促进下与二芳基二硒醚或二硫醚在DMSO中发生选择性C-H官能化反应，成功构建了3-单硒化、1,3-双硒化以及1-硫化产物。通过调节底物比例和温度，可精确控制反应位点与取代模式，产率可达24%-85%。该反应无需过渡金属催化，条件绿色，且可以适用于杂环硫醇（如噻吩硫醇）。单晶X射线衍射证实了产物的结构，克级实验（产率84%）和衍生化（如钯催化偶联）进一步凸显其合成价值。
炔基C-H芳硫化反应，主要有碱作用和氧化剂作用两个体系。碱促进的反应体系是在乙腈中使用咪唑对1-苯乙炔基吡咯并[1,2-a]喹喔啉与芳基硫醇进行选择性芳基硫化反应，生成(Z)-或(E)-乙烯基硫醚，产率在75%至95%之间，Z/E比例从10:1到1:1不等。使用(NH4)2S2O8介导的二苯基二硒化物或硫酚与吡咯并[1,2-a]喹喔啉炔烃进行的C-H芳基硒化反应，在室温下，进行45 min就就可以生成(E)-构型的二硒化产物和(Z)-或(E)-乙烯基硫醚，产率在70%至85%之间。该方法表现出很强的兼容性，并能适应复杂的底物，且可通过进一步衍生化反应，因此所得产物展现出广泛的多功能性。
铜促进的C1-H胺化反应则利用六氟磷酸四乙腈铜（[Cu(MeCN)4]PF6）进行催化，以N-氟代双苯磺酰胺（NFSI）为胺化试剂，实现吡咯并[1,2-a]喹喔啉的C1位直接胺化反应。反应在100 ℃下30 min内完成，产率高达96%，且对7-、8-位取代基及4-芳基取代底物均表现出良好的耐受性。克级实验验证了其实际应用潜力，且产物可进一步衍生化进行硫氰化或碘化反应，为药物分子修饰提供了新途径。
 

Pyrrolo[1,2-a]quinoxalines are a class of heterocyclic compounds with significant biological activities and rigid structures, demonstrating broad application potential in drug development (e.g., antitumor, antidiabetic, antimalarial) and materials science (e.g., organic light-emitting diodes, sensors, organic solar cells). However, traditional synthetic methods for their core structures often suffer from low selectivity, multiple steps, and difficulties in precisely constructing multi-substituted derivatives. This thesis focuses on C-H activation reactions, developing a series of green and efficient synthetic methods to successfully achieve arylation, amination, selenation, sulfuration, and alkenylation of pyrrolo[1,2-a]quinoxalines.
Palladium-catalyzed C-H arylation reactions were conducted using palladium acetate as the catalyst, in synergy with the X-Phos ligand, in toluene solvent, achieving direct C-H arylation of pyrrolo[1,2-a]quinoxalines with aryl iodides. By adjusting substrate ratios and steric hindrance, selective synthesis of mono-arylated (C1 position) or di-arylated (C1 and C3 positions) products was achieved with yields ranging from 44% to 88%. The reaction conditions are mild, with broad substrate compatibility, accommodating both electron-donating and electron-withdrawing groups, and scalable to gram-scale preparation (yield 65%).
Palladium-catalyzed C-H alkenylation reactions also utilized palladium acetate as the catalyst, interacting with the ligand L-pyroglutamic acid, to achieve C3-H alkenylation of pyrrolo[1,2-a]quinoxalines with allyl esters (such as ethyl acrylate and adamantane-derived esters) in acetic acid, yielding 81%. Coupling with bioactive molecules like L-menthol derivatives was also successfully achieved.
C-H selenation/sulfuration reactions of pyrrolo[1,2-a]quinoxalines were promoted by iodine (I2), selectively functionalizing C-H bonds with diaryl diselenides or disulfides in DMSO, successfully constructing 3-monoselenated, 1,3-diselenated, and 1-sulfurated products. By adjusting substrate ratios and temperature, reaction sites and substitution patterns could be precisely controlled, with yields ranging from 24% to 85%. This reaction does not require transition metal catalysis, features green conditions, and is applicable to heterocyclic thiols (e.g., thiophene thiol). Single-crystal X-ray diffraction confirmed the product structures, and gram-scale experiments (yield 84%) and derivatization (e.g., palladium-catalyzed coupling) further highlighted their synthetic value.
Alkyne C-H arylthiolation reactions primarily involve two systems: base-promoted and oxidant-promoted. The base-promoted system uses imidazole in acetonitrile to selectively arylthiolate 1-phenylethynylpyrrolo[1,2-a]quinoxalines with aryl thiols, generating (Z)- or (E)-vinyl sulfides with yields between 75% and 95%, and Z/E ratios ranging from 10:1 to 1:1. The (NH4)2S2O8-mediated system with diphenyl diselenides or thiophenols and pyrrolo[1,2-a]quinoxaline alkynes at room temperature for 45 minutes produced (E)-configured diselenated products and (Z)- or (E)-vinyl sulfides with yields between 70% and 85%. This method shows strong compatibility and adaptability to complex substrates, with further derivatization potential, thus the products exhibit broad versatility.
Copper-promoted C1-H amination reactions utilized tetrakis(acetonitrile)copper(I) hexafluorophosphate ([Cu(MeCN)4]PF6) as the catalyst, with N-fluorobenzenesulfonimide (NFSI) as the amination reagent, achieving direct C1 amination of pyrrolo[1,2-a]quinoxalines. The reaction completed within 30 minutes at 100 °C with yields up to 96%, showing good tolerance to 7-, 8-position substituents and 4-aryl substituted substrates. Gram-scale experiments verified its practical application potential, and further derivatization for thiocyanation or iodination provided new pathways for drug molecule modification.
This study proposes a multifunctional reaction system for C-H activation of pyrrolo[1,2-a]quinoxalines, significantly enhancing synthetic efficiency and structural diversity. All methods demonstrate simplicity, mild reaction conditions, and broad substrate compatibility, validated through gram-scale reactions and derivatization experiments. Future research will delve into reaction mechanisms, expand substrate options, and explore applications in natural products, drug synthesis, and materials.
 

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