Direct Metal-Free Synthesis of β-Keto and Dienyl Sulfides from Bromopenta-1,4-dienes and Thiols

In sulfur chemistry, interconverting sulfur radicals and anions is essential yet challenging due to their high reactivity and transient nature. Herein, we show that thiophenols and thiols can be selectively directed to form distinct intermediates matched with different C=C bonds in nonconjugated 1,4-dienes, enabling tunable reaction selectivity at room temperature. This metal-free method provides efficient access to various β-keto and dienyl sulfides in moderate to good yields.