New mode of sulfur ylides reactivity: stereoelectronic control provides C–C bond insertion before cyclopropanation/epoxidation directly affording homologated three-membered rings

New mode of sulfur ylides reactivity: stereoelectronic control provides C–C bond insertion before cyclopropanation/epoxidation directly affording homologated three-membered rings Full article

Journal

Organic Chemistry Frontiers
ISSN: 2052-4110 , E-ISSN: 2052-4129

Output data

Year: 2025, Volume: 12, Number: 24, Pages: 6852-6863 Pages count : 12 DOI: 10.1039/d5qo01266j

Authors

Shorokhov Vitaly V. ¹ , Chabuka Beauty K. ² , Nikolaeva Albina A. ¹ , Zhokhov Sergey S. ¹ , Andreev Ivan A. ³ , Ratmanova Nina K. ³ , Trushkov Igor V. ³ , Ivanova Olga A. ¹ , Alabugin Igor V. ²

Affiliations

1	Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie gory 1-3, Moscow 119991, Russia
2	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA
3	N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Leninsky pr. 47, Moscow 119991, Russia

Ylides are versatile reagents known for their dual electrophilic and nucleophilic reactivity, mimicking carbenes in many reactions. In this study, we uncover a previously unreported reactivity pathway for ylides: a methylene insertion into C–C bonds. We show that sulfur ylides can achieve homologation of alkenes and aldehydes before proceeding through the classical Corey–Chaykovsky reaction. This process allows for the dual transfer of CH2 groups to both substrates, yielding benzylcyclopropanes and benzyloxiranes, valuable intermediates in organic synthesis. Remarkably, the same sulfur ylide reagent participates in two distinct carbene-like transformations within this cascade. Mechanistic studies reveal the role of a tightly coordinated stereoelectronic network playing a crucial role in facilitating anionic 1,2-aryl shifts.

Shorokhov V.V. , Chabuka B.K. , Nikolaeva A.A. , Zhokhov S.S. , Andreev I.A. , Ratmanova N.K. , Trushkov I.V. , Ivanova O.A. , Alabugin I.V.
New mode of sulfur ylides reactivity: stereoelectronic control provides C–C bond insertion before cyclopropanation/epoxidation directly affording homologated three-membered rings
Organic Chemistry Frontiers. 2025. V.12. N24. P.6852-6863. DOI: 10.1039/d5qo01266j WOS Scopus

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