铜催化的二醇类化合物自由基对映选择性去对称化反应研究

手性含氧化合物广泛存在于药物分子、生物活性物质和天然产物中，这类化 合物的高效合成有着重要的应用价值。在众多构建方法中，二醇化合物的对映选 择性去对称化策略日益受到关注，其原因在于该策略有着底物易合成、反应类型 多样、便于构建季碳手性中心等优点，但目前基于离子型反应机理的对映选择性 去对称化报道存在底物适用范围窄、官能团兼容性有限、全碳季碳手性中心构建 少等局限。与之对应的，自由基反应具有活性高、官能团兼容性广、受空间位阻 影响小等特点，但自由基的立体选择性控制是现代有机合成领域极具挑战性的课 题之一，文献报道中尚未实现自由基参与的催化对映选择性去对称化反应。针对 这一挑战性课题，本论文通过发展不同铜催化体系，系统性研究了几类高活性自 由基与二醇类化合物的对映选择性去对称化反应，发展了手性含氧化合物合成的 新方法，实现了几类极具合成挑战性的季碳手性中心的高对映选择性构建，为高 活性自由基的立体选择性控制提供了新思路。主要内容如下： 以高活性烷基 π 自由基的立体选择性控制为研究目标，设计了铜/手性磷酸的 协同催化体系，通过催化剂与原位产生的烷基自由基物种之间紧密的相互作用， 实现了自由基参与的催化对映选择性去对称化新反应。该反应采用前手性烯基二 醇化合物作为反应底物，通过全氟烷基磺酰氯产生的全氟烷基自由基与烯烃发生 自由基加成实现反应的启动，反应中需要加入碳酸银作为添加剂，用以中和副产 物盐酸，从而抑制非手性背景反应的发生。该反应官能团兼容性好、反应条件温 和，在两个手性中心位置不仅兼容吸电子/给电子基团取代的苯环，而且兼容呋喃、 噻吩等芳杂环，能以最高 96%的收率、最高 >20:1 的非对映选择性和最高 97%的 对映选择性获得目标手性产物。反应产物通过衍生化可以一步合成手性螺杂环化 合物。成功为含两个季碳手性中心的四氢呋喃类化合物的高效构筑提供了新方法。 以酰基 σ 自由基的远程立体选择性控制为研究目标，设计了铜/手性二齿磺酰 胺配体催化体系，通过与二醇类化合物分子间的对映选择性去对称化反应，实现 了这一活性 σ 自由基的远程立体选择性控制。该反应以简单易得的（杂）芳基、 烷基醛作为高原子经济性酰基自由基前体，兼容包括前手性 1,3-二醇、2-胺基1,3-二醇、1,2,3-三醇以及部分羟基被保护的内消旋四醇在内的多种醇类化合物。 以最高 89%的收率、最高 98%的对映选择性高效构建了全碳、含氧、含氮和含氯 季碳手性中心骨架。反应产物可以进一步衍生化为手性三碳合成子、α,α-双取代手性非天然氨基酸，展现了该催化策略的应用价值。控制实验证明酰基自由基参 与了手性控制步骤并排除了可能的离子型反应机理，该反应为高活性 σ 自由基的 对映选择性控制提供了新方法。 以磺酰基 σ自由基参与的对映选择性杂原子–杂原子交叉偶联反应为研究目标， 利用铜/手性双齿磺酰胺配体催化体系，通过自由基单电子还原消除的外球反应机 理，避免了杂原子难以双电子还原消除这一难题，实现了对映选择性硫–氧杂原 子交叉偶联反应。该反应普适性好，能够兼容前手性 1,3-二醇、内消旋 1,2-二醇 以及 1,2,3-三醇等醇类化合物，以最高 97%的反应收率、最高 99%的对映选择性 构建了全碳和含氧的季碳手性中心骨架。机理实验研究表明反应手性控制涉及磺 酰基自由基历程，控制实验说明碳酸银与质子海绵通过淬灭反应产生的盐酸，提 高了反应效率和对映选择性。在反应的应用性上，成功将甘油这一大宗化工原料 直接应用于该催化体系，并实现了克级规模转化。甘油经一步催化反应即可得到 高对映选择性的手性产物，通过简单衍生化可以得到多种重要的手性三碳合成子， 实现了甘油的高附加值转化。特别是使用 71%纯度的工业粗甘油也能实现高对映 选择性控制（82% ee）。 此外还完成了抗真菌药关键中间体以及药物左羟丙哌嗪的 合成，证明了该反应潜在的应用价值。 

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