Recently, the research group led by Professor Liu Weiping, a specially appointed research fellow at the College of Chemistry and Chemical Engineering, has made new progress in the field of manganese-catalyzed borrowing hydrogen reactions. This work was recently published in the internationally renowned journal Nature Communications, titled Manganese-catalyzed cyclopropanation of allylic alcohols with sulfones.
Cyclopropanes are among the most important structural units in natural products, pharmaceuticals, and agrochemicals. The incorporation of cyclopropanes into biologically active molecules can allow fine-tuning of metabolic stability, enhancement of their potency, and reduction of off-target effects. Moreover, cyclopropyl fragments are also commonly used as versatile building blocks in organic synthesis and as radical clocks in mechanistic investigations.
The team has reported a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones as carbene alternative precursors via a borrowing hydrogen strategy under mild conditions. Various allylic alcohols and arylmethyl trifluoromethyl sulfones work efficiently in this borrowing hydrogen transformation and thereby deliver the corresponding cyclopropylmethanol products in 58% to 99% yields. Importantly, a major benefit of this transformation is that the versatile free alcohol moiety is retained in the resultant products, which can undergo a wide range of downstream transformations to provide access to a series of functional molecules. Mechanistic studies support a sequential reaction mechanism that involves catalytic dehydrogenation, Michael addition, cyclization, and catalytic hydrogenation.
The first author of the paper is Yu Ke, a 2024 doctoral graduate from the College of Chemistry and Chemical Engineering. The co-authors of the paper are Nie Qin, a doctoral student, and Chen Qianjin, a research fellow. The corresponding author of the paper is Professor Liu Weiping, a specially appointed research fellow. Donghua University is the sole corresponding institution.
Paper link: https://www.nature.com/articles/s41467-024-51188-x#Sec3
