Fig. 4

Folding radical cascades involving 1,5-HAT and activation of a secondary alkyl group. A samarium(II) folding cascade involving 1,5-HAT activation of secondary alkyl groups in key radical intermediates V is shown. a Scope of the samarium(II) folding cascade involving activation of a secondary alkyl group by 1,5-HAT to give products 7d–j. b The mechanism of folding involves 1,5-HAT in key radical intermediates V to give 9. A 1,2-ester shift then generates radical intermediates 10 that, after hemiketal opening and SET reduction, give samarium(III) enolates 12. The final products 7d–j are obtained by lactonisation of enolates 12