A Mechanochemical, Catalyst‐Free Cascade Synthesis of 1,3‐Diols and 1,4‐Iodoalcohols Using Styrenes and Hypervalent Iodine Reagents

Abstract

A mechanochemical and solvent/catalyst-free functionalization of olefins with hypervalent iodine reagents has been developed, enabling the synthesis of 1,3-dioxygenated compounds. Under similar reaction conditions with the addition of molecular iodine, 1,4iodoalcohols can be synthesized. These valuable products are non-trivial to achieve via standard solutionphase methods. Mechanistic study reveals that the hypervalent iodine reagent might dimerize at solid state with the help of mechanical force. The active monomeric form of hypervalent iodine reagent might trigger the 1,3and 1,4-difunctionalization reactions in an intermolecular cascade manner.

Intermediates in Mechanochemical Reactions

“…Other cases of unexpected in situ force‐driven transformations of reactants with implication in the selectivity of the process have also been documented [61] …”

Solvent-free synthesis of organic electrodes for green sustainable energy storage

“…Recently, Pan et al synthesized 1,3-diols and 1,4-iodoalcohols, which were difficult to be synthesized by solution-based method, and with the aid of ball milling, solvent-free synthesis of 1,3-diols and 1,4-iodoalcohols was achieved. 19 Nowadays, more and more researchers have noticed this new green synthesis method. The solvent-free synthesis of organic materials can be easily mass-produced and is environment-friendly, and it is a good choice to apply them to prepare organic electrode materials so as to decrease their cost and promote their practical application.…”

Phenyliodine bis(trifluoroacetate) as a sustainable reagent: exploring its significance in organic synthesis

“…Pan et al 183 have developed a mechanochemical and solvent/catalyst-free method for functionalizing olefins 286 using PIFA reagents, facilitating the synthesis of 1,3-dioxygenated compounds 287 (Scheme 110) and 1,4-iodoalcohols 289 (Scheme 111). The process, challenging with conventional methods, involves an intermolecular cascade triggered by the active monomeric form of PIFA through an ionic pathway, as revealed by mechanistic studies.…”