Some aspects of radical chemistry in the assembly of complex molecular architectures

Abstract

SummaryThis review article describes briefly some of the radical processes developed in the authors’ laboratory as they pertain to the concise assembly of complex molecular scaffolds. The emphasis is placed on the use of nitrogen-centred radicals, on the degenerate addition–transfer of xanthates, especially on its potential for intermolecular carbon–carbon bond formation, and on the generation and capture of radicals through electron transfer processes.

Regioselective C−H Xanthylation as a Platform for Polyolefin Functionalization

“…We view xanthylated polyolefins as am aterial platform for accessing diverse,functional materials that unlock arange of new polymer properties.T his is in contrast to previous methods targeting the introduction of as ingle functional group,with new C À Htransformations required for each new desired derivative.T his approach takes advantage of the remarkable versatility of alkyl xanthates in both radicalmediated and polar bond-forming reactions. [24] Fore xample, reagents recently developed by Shen and co-workers enable ao ne-step introduction of the trifluoromethylthiol group (2). [25] This functional group,w ell known to modulate the lipophilicity of medicinal compounds,i su nderexplored in polymer chemistry.F urthermore,t he xanthate group was used directly as ac hain-transfer agent for the reversible addition fragmentation chain transfer (RAFT) polymerization of vinyl acetate (3).…”

Design of Leaving Groups in Radical CC Fragmentations: Through‐Bond 2c–3e Interactions in Self‐Terminating Radical Cascades

“…In self‐terminating cascades, introduced by Wille et al., stable fragmenting radicals exit the reaction without participating in subsequent transformations 10f. Only a few such processes involve CC bond scission with the formation of C‐centered radicals 10g–j…”

Lawsone in organic synthesis

“…171,172 The reaction of 1 with radical species was one of the first radical methods employed to obtain C- and catalytic amounts of silver nitrate. 171,172 The reaction of 1 with radical species was one of the first radical methods employed to obtain C- and catalytic amounts of silver nitrate.…”