A method for the direct asymmetric α-sulfenylation of aldehydes with sulfides was developed. By merging electrochemistry and asymmetric organocatalysis, we obtained α-sulfenylated aldehydes with good to excellent enantioselectivities. Mechanistic investigations indicated a pivotal role of iodine as a catalytic mediator, not only facilitating redox transformations but also possibly contributing to the formation of sulfenyl iodide (RSI) intermediates derived from electrochemically generated disulfides. Our metal-free protocol offers a sustainable and efficient route to access a wide array of α-sulfenylated aldehydes. Remarkably, these transformations take place at room temperature, obviating the need for additional stoichiometric oxidants, thus exemplifying an environmentally friendly and practical synthetic strategy.
