Although sulfoxide is an important structural motif found in biological molecules and prevalent feedstocks in synthetic chemistry, a general and sustainable access route to (Z)-α,β-unsaturated sulfoxides remains highlychallenging due to the thermodynamic instability of Z-type geometric and the notorious sulfur nucleophiles poisoning of metal catalyst. Here we report a new protocol based on homogeneous octamolybdate-catalyzed anti-hydrothiolation and after Z-retentive sulfoxidation methodology, allowing access to (Z)-α,β-unsaturated sulfoxides from commercially available alkynes, thiols and H2O2. Control experiment investigations indicate that the molecular molybdenum is a thiyl radical initiator, Z-type geometric mediator and sulfoxidation catalyst. Notably, this one-pot reaction features broad substrate scopes with high stereoselectivity (Z/E up to > 99:1) and mild reaction conditions, thus providing a promising approach for the preparation of Z-vinyl sulfoxide compounds.

中文翻译：

---

由多功能八钼酸盐实现炔烃与硫醇和过氧化氢的 Z 选择性硫化氢


尽管亚砜是生物分子中发现的重要结构基序，也是合成化学中普遍的原料，但由于 Z 型几何的热力学不稳定性和金属催化剂臭名昭著的亲硫试剂中毒，获得 （Z）-α，β-不饱和亚砜的一般和可持续途径仍然极具挑战性。在这里，我们报告了一种基于均相八钼酸盐催化的抗氢硫醇化和 Z 保留硫氧化方法的新方案，允许从市售炔烃、硫醇和 H 2 O 2 中获得 （Z）-α，β-不饱和亚砜。对照实验研究表明，分子钼是巯基自由基引发剂、Z 型几何介质和硫氧化催化剂。值得注意的是，这种一锅反应具有广泛的底物范围、高立体选择性（Z/E 高达 > 99：1）和温和的反应条件，因此为制备 Z-乙烯基亚砜化合物提供了一种有前途的方法。