轴手性联芳基化合物的芳基化构建策略研究

    轴手性联芳基骨架广泛存在于具有重要生物活性的天然产物以及药物分子中，它们作为核心载体被用于构建一系列不对称催化领域的优势配体与催化剂。其中，基于联芳基骨架的非C2对称性联芳基二酚的合成方法报道相对较少，自偶联反应的存在使得现有的方法具有明显局限性。另一方面，含氮杂环联芳烃化合物主要是通过过渡金属催化的交叉偶联反应和光催化的芳基自由基对吡啶的加成反应合成，但是反应条件苛刻、氮杂环与金属配位造成催化剂失活、吡啶的区域选择性等问题导致反应效率较低。因此，开发高效、高选择性的方法用于非C2对称性联芳基二酚和含氮杂环联芳烃化合物的合成具有较高的学术研究价值和广阔的应用前景。光氧化还原催化作为一种可以在温和条件下产生芳基自由基的方法，可实现丰富多样的芳基化过程。本论文的研究内容是借助有机小分子催化或光氧化还原催化的手段，通过芳基化策略实现了多种联芳基骨架的构筑，主要内容包括：
    研究了利用手性磷酸催化对苯醌与2-萘酚的芳基化反应与“一锅法”氧化，实现轴手性芳基醌化合物的高效、高对映选择性合成（产率最高可达75%，ee最高可达96%）。以该类化合物作为平台分子，可以与多种类型的亲核试剂发生官能团化过程，包括芳基硫酚、二芳基氧膦、吲哚、-酮酯，实现了结构复杂多样的非C2对称性联芳基二酚的高效合成，丰富了该类轴手性化合物的分子库。值得一提的是，在该转化过程中，芳基醌的对映选择性均能得到保持。以吲哚为亲核试剂，得到的产物可被再次氧化得到芳基醌化合物，有利于进一步进行后期结构修饰。此方法不仅构建了新颖的轴手性芳基醌骨架，也为非C2对称性联芳基二酚的合成提供了一条新的途径。
    研究了在光氧化还原催化体系中，以1-溴-2-萘酚作为芳基自由基前体，通过芳基化过程实现了C1对称性1,1’-联萘-2,2’-二酚（BINOL）的高效合成，产率最高可达80%。与已报道的合成方法相比，该方法较好地改善了底物普适性和官能团兼容性。该策略可以有效地避免自偶联副反应，对于带有不同取代基的两类底物的光催化芳基化反应也均可顺利进行。
    研究了该光催化体系所展现的对2-萘胺类底物的很好的兼容性，可在无保护基或导向基的条件下一步构建2-氨基-2’-羟基-1,1’-联萘（NOBIN）骨架，产率最高达64%。光催化剂负载量降至0.1 mol%的条件下也可以高效实现C1对称性BINOL的克级规模合成（产率75%）。之后，设计了自由基捕获、荧光淬灭、循环伏安等一系列机理验证实验，并根据实验结果提出了合理的反应机理，即芳基自由基与2-萘酚加成后再经历单电子转移与芳构化过程得到目标产物。在此基础上，通过氢键催化、相转移催化、过渡金属催化等策略进行了光催化不对称合成C1对称性BINOL的初步尝试。
    研究了在光催化下通过溴代氮杂芳烃和苯酚的交叉偶联反应，实现含氮杂环联芳烃化合物的合成。利用质子耦合电子转移策略，在溴代氮杂芳烃质子化过程中会同时发生底物与光催化剂的单电子转移过程，得到的氮杂芳基自由基可以与体系中的苯酚类底物发生交叉偶联反应，产率最高可达83%。苯酚类底物同时作为芳基化试剂与质子供体参与反应。该方法具有良好的官能团兼容性，例如卤素、酯基、氰基、三氟甲基、烷基、烷氧基等，并且原料简单易得、反应操作简单。对于不含酚羟基的芳烃类底物，通过引入其它可实现溴代氮杂芳烃质子化的质子给体，例如以六氟异丙醇作为溶剂，同样能够实现含氮杂环联芳烃化合物的高效合成（产率最高可达91%）。

Axially chiral biaryl skeletons are widely found in bioactive natural products and drug candidates. In asymmetric catalysis, ligands and catalysts built on chiral biaryl cores find wide applications across many mechanistically distinct transformations. Within this compound class, there are relatively few reports on non-C₂-symmetric biaryldiols. Their restrictios arise mainly from the prevailing homo-coupling reactivity in aryl-aryl coupling reactions. On the other hand, the preparation of N-heterobiaryls mainly relies on transition metal-catalyzed cross-coupling reactions and photocatalytic addition of aryl radicals to pyridines. However, the efficiency of these schemes could be hampered by harsh reaction conditions required, deactivation of metal catalyst due to competing coordination of N-heterocycles, as well as regioselectivity issue in radical addition to pyridines. Therefore, the development of highly efficient and selective methods for the synthesis of non-C₂-symmetric biaryldiols and N-heterobiaryls is of high research value and practical utility. Photoredox catalysis-enabled diverse arylation reactions with aryl radicals under mild reaction conditions. The research of this thesis realizes the construction of multiple classes of biaryls through arylation process promoted by organocatalysis or photoredox catalysis. The main contents include:

Highly efficient and enantioselective synthesis of axially chiral aryl-p-quinones has been achieved through arylation of benzoquinones with 2-naphthols via chiral phosphoric acid (CPA) catalysis and “one-pot” oxidation (yield up to 75% and ee up to 96%). Notably, aryl-p-quinones represent one class of platform molecules: they were amenable to downstream functionalization by myriad nucleophiles including aryl thiophenols, diarylphosphine oxides, indoles and b-keto esters with almost perfect preservation of enantioselectivities. This method allows rapid population of related chemical space with highly functionalized and structurally diverse axially chiral biaryldiols. The application of indole nucleophiles would regenerate the aryl-p-quinones after a re-oxidation event, thus enabling another follow-up synthetic elaboration. Overall, this method provides novel skeletons of axially chiral aryl-p-quinones and offers new pathway for the synthesis of non-C₂-symmetric biaryldiols.

With 1-bromo-2-naphthols as aryl radical precursors, the highly efficient synthesis of C₁-symmetric 1,1'-bi-2-naphthol (BINOL) has been realized via arylation pathway enabled by photoredox catalysis with up to 80% yield. Compared to previous methods, this strategy could effectively improve the substrate scope and exhibited good tolerance of functional groups. The homo-coupling side reactions were successfully circumvented in this photocatalytic system. The photocatalytic arylation process worked smoothly for both coupling partners that bear various functionalities.

2-Naphthylamines are another class of compatible coupling partners under this photocatalytic system, hence establishing the protecting- or directing group-free synthesis of 2-amino-2'-hydroxy-1,1'-binaphthyls (NOBINs) in one step with up to 64% yield. Highly efficient synthesis of C₁-symmetric BINOLs on gram-scale could be achieved with photocatalyst loading as low as 0.1 mol% (75% yield). A plausible mechanism was proposed on the basis of a series of mechanistic experiments, including radical trapping, luminescent quenching and cyclic voltammetry experiments, in which the product can be obtained through the aryl radical addition to 2-naphthols, followed by single electron transfer and rearomatization. This proposed mechanism served as basis for the preliminary studies conducted to develop photocatalytic asymmetric synthesis of C₁-symmetric BINOLs by means of H-bonding catalysis, phase transfer catalysis and transition metal catalysis.

The photocatalysis also underpinned the cross-coupling reactions of bromoazaarenes with phenols for the synthesis of N-heterobiaryls. In this proton-coupled electron transfer strategy, protonation of bromoazaarenes and the coupled single electron transfer process with photocatalyst would release the azaarene radicals that undergo cross-coupling with phenols in up to 83% yield. The phenol derivatives could be both substrates and proton donors in this transformation. A diverse range of functional groups, such as halogen, ester, cyano, trifluoromethyl, alkyl, alkoxy and so on were found compatible with the established conditions. The operational simplicity and commercial availability of all substrates greatly broaden the appeal of this reaction. For arenes without phenolic hydroxyl group, the construction of N-heterobiaryls could be accomplished by introducing other proton donors. To this end, hexafluoroisopropanol applied as solvent also fulfilled the protonation of bromoazaarenes, generating the corresponding N-heterobiaryls in up to 91% yield.

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