General Deoxygenative Strategy for the Synthesis of Isothiocyanates and Thiocyanates

Given the prominent role of organic isothiocyanates and thiocyanates as versatile building blocks in organic synthesis, we report herein a general and efficient deoxygenative functionalization strategy that exploits readily available and inexpensive carboxylic acids and alcohols as starting materials, with triphenylphosphine serving as the deoxygenative reagent. This protocol delivers the corresponding isothiocyanates and thiocyanates in good yields and accommodates a broad substrate scope encompassing structurally complex carboxylic acids and bioactive natural alcohols. Moreover, the resulting products can be readily diversified into a wide array of high‐value‐added organosulfur compounds, underscoring the synthetic utility of this approach.