749920-60-3Relevant academic research and scientific papers
Alkene Carboarylation through Catalyst-Free, Visible Light-Mediated Smiles Rearrangement
Whalley, David M.,Duong, Hung A.,Greaney, Michael F.
, p. 1927 - 1930 (2019)
A light-mediated Truce–Smiles arylative rearrangement is described that proceeds in the absence of any photocatalyst. The protocol creates two C?C bonds from simple starting materials, with the installation of an aryl ring and a difluoroacetate moiety across unactivated alkenes. The reaction proceeds via a radical mechanism, utilizing a light-mediated reduction of ethyl bromodifluoroacetate by N,N,N′,N′-tetramethylethylenediamine (TMEDA) to set up intermolecular addition to an unactivated alkene, followed by Truce–Smiles rearrangement.
Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
supporting information, p. 9729 - 9736 (2021/07/19)
Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs; the newly formed C-I bond in these products is then functionalized via a silyl-mediated Giese reaction. This chemistry also translates smoothly to 1,3-disubstituted iodo-BCPs. A wide variety of radical acceptors and iodo-BCPAs are accommodated, providing straightforward access to an array of valuable aniline-like isosteres.
