Sulfur stereogenic molecules have a significant impact on drug development. Among them, sulfilimines are chiral molecules bearing S(IV) stereocentres, which exhibit great value in chemistry and biology but have so far been synthetically challenging to achieve. Similarly, it has also been a challenge to control the stereochemistry in Chan–Lam coupling, which has been widely used to construct C–N, C–O and C–S bonds by coupling nucleophiles with boronic acids using copper complexes. Here we report a highly chemoselective and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids to deliver an array of thermodynamically disfavoured aryl sulfilimines containing a sulfur stereocentre. A copper catalyst from a 2-pyridyl N-phenyl dihydroimidazole ligand has been designed that enables effective enantiocontrol by means of a well-defined chiral environment and high reactivity that outcompetes the background racemic transformation. A combined experimental and computational study establishes the reaction mechanism and unveils the origin of chemoselectivity and stereoselectivity.

硫立体分子对药物开发具有重大影响。其中，硫亚胺是带有S(IV)立构中心的手性分子，在化学和生物学中表现出巨大的价值，但迄今为止在合成上仍具有挑战性。同样，控制 Chan-Lam 偶联中的立体化学也是一个挑战，该偶联已广泛用于通过使用铜配合物将亲核试剂与硼酸偶联来构建 C-N、C-O 和 C-S 键。在这里，我们报道了次磺酰胺与芳基硼酸的高度化学选择性和对映选择性Chan-Lam S-芳基化，以产生一系列含有硫立构中心的热力学不利的芳基硫亚胺。设计了一种来自 2-吡啶基N-苯基二氢咪唑配体的铜催化剂，通过明确的手性环境和超越背景外消旋转化的高反应性，实现有效的对映体控制。实验和计算相结合的研究建立了反应机理并揭示了化学选择性和立体选择性的起源。