Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development of a catalytic, easily tunable synthetic approach for the stereodivergent synthesis of both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report a photoredox and nickel dual catalytic strategy for the stereodivergent sulfonylalkenylation of terminal alkynes with vinyl triflates and sodium sulfinates under mild conditions. With a judicious choice of simple nickel catalyst and ligand, this method enables efficient and divergent access to both Z- and E-sulfonyl-1,3-dienes from the same set of simple starting materials. This method features broad substrate scope, good functional compatibility, and excellent chemo-, regio-, and stereoselectivity. Experimental and DFT mechanistic studies offer insights into the observed divergent stereoselectivity controlled by ligands.

功能化烯烃的精确立体控制是有机合成中一个长期存在的研究课题。然而，用于从普通底物中立体发散合成E选择性和更具挑战性的Z选择性高取代 1,3-二烯的催化、易于调节的合成方法的开发仍未得到充分开发。在这里，我们报告了一种光氧化还原和镍双重催化策略，用于在温和条件下用三氟甲磺酸乙烯酯和亚磺酸钠对末端炔烃进行立体发散磺酰基烯基化反应。通过明智地选择简单的镍催化剂和配体，该方法能够有效和不同地访问Z-和E-来自同一组简单起始材料的磺酰基-1,3-二烯。该方法具有广泛的底物范围、良好的功能相容性以及出色的化学选择性、区域选择性和立体选择性。实验和 DFT 机理研究提供了对观察到的由配体控制的发散立体选择性的见解。