Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines.
Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines.
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DOI：
10.1021/jacs.2c04627
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发表时间：
2022-07-13
影响因子：
15
通讯作者：
Jia, Tiezheng
中科院分区：
文献类型：
--
作者：
Meng, Tingting;Wells, Lucille A.;Wang, Tianxin;Wang, Jinyu;Zhang, Shishuo;Wang, Jie;Kozlowski, Marisa C.;Jia, Tiezheng
受到 IV 型胶原蛋白网络中 S=N 键的发现及其在稳定基底膜中的重要作用的启发，硫亚胺在化学和生物学领域引起了广泛关注。然而，由于缺乏在生物分子相容条件下构建硫亚胺的温和、高效和环境友好的方案，其进一步的应用受到阻碍。在这里，我们报道了游离二芳基硫亚胺与芳基硼酸的无末端氧化剂铜催化脱氢 Chan-Lam 偶联，具有优异的化学选择性和广泛的底物兼容性。温和的反应条件和生物分子相容性允许该方案在复杂肽的后期功能化中使用，更重要的是，作为模型蛋白质中展示的有效的生物共轭方法。实验和计算机制相结合的研究表明，内球电子转移过程规避了传统 Chan-Lam 偶联反应中使用的牺牲氧化剂。找到了一条能量上可行的协同途径，其中氢化铜促进氢原子从异丙醇溶剂中提取，从而通过四元过渡态产生氢气。
Inspired by the discovery of an S=N bond in the collagen IV network and its essential role in stabilizing basement membranes, sulfilimines have drawn much attention in the fields of chemistry and biology. However, its further uptake is hindered by the lack of mild, efficient and environmentally benign protocols by which sulfilimines can be constructed under biomolecule-compatible conditions. Here, we report a terminal oxidant-free copper-catalyzed dehydrogenative Chan-Lam coupling of free diaryl sulfilimines with arylboronic acids with excellent chemoselectivity and broad substrate compatibility. The mild reaction conditions and biomolecule-compatible nature allow the employment of this protocol in the late-stage functionalization of complex peptides, and more importantly, as an effective bioconjugation method as showcased in a model protein. A combined experimental and computational mechanistic investigation reveals an inner sphere electron transfer process circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions. An energetically viable concerted pathway was located wherein a copper hydride facilitates hydrogen atom abstraction from the isopropanol solvent to produce dihydrogen via a four-membered transition state.
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