Manganese-catalyzed cyclopropanation of allylic alcohols with sulfones

• Published in: Nature communications Vol. 15; no. 1; pp. 6798 - 8
• Main Authors: Yu, Ke, Nie, Qin, Chen, Qianjin, Liu, Weiping
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 09.08.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/403/933; 639/638/403/934; 639/638/77/888; Agrochemicals; Alcohol; Alcohols; Alkenes; Carbenes; Cyclopropane; Dehydrogenation; Humanities and Social Sciences; Hydrogen; Manganese; multidisciplinary; Natural products; Organic compounds; Reaction mechanisms; Reagents; Science; Science (multidisciplinary); Sulfones
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-51188-x

Cyclopropanes are among the most important structural units in natural products, pharmaceuticals, and agrochemicals. Herein, we report 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. Developing readily available and bench-stable reagents for the cyclopropanation of olefins is needed as traditional methodologies mainly rely on carbene-based strategies. Herein, the authors report a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones via a borrowing hydrogen strategy under mild conditions.