Unmasked Primary Amines as C-Nucleophiles for Catalytic C–C Bond-Formation

Abstract

A practical, catalytic entry to α,α,α‑trisubstituted (α‑tertiary) primary amines by C–H functionalisation has long been recognised as a critical gap in the synthetic toolbox. We report a simple and scalable solution to this problem that does not require any <i>in situ</i> protection of the amino group and proceeds with 100% atom-economy. Our strategy, which uses an organic photocatalyst in combination with azide ion as a hydrogen atom transfer (HAT) catalyst, provides a direct synthesis of <i>C</i>-alkylated amines or γ‑lactams, including valuable azaspirocycles. We anticipate that this methodology will inspire new retrosynthetic disconnections for substituted amine derivatives in organic synthesis, and particularly for challenging α‑tertiary primary amines.

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates

“…Significantly, the formation of the key conjugated N-acyliminium intermediate using these photoredox conditions can be seen as complementary to the well-developed electrophilic activation modes of allenamides. We are currently examining the full mechanism of this transformation, expanding the scope of substrates that can be used in the radical addition step, and alternative fates for the α-N-acyl radical 13 [58][59][60].…”

Environmentally Sustainable Solvent-based Process Chemistry for Metals in Printed Circuit Boards

“…To this end, a rheology modifier utilising polyethylene glycols (PEGs) was mixed with the DESs at elevated temperature and left to cool forming a thick, gel like substance. 39 A Reline solder paste, containing 88.5 wt% SAC305 (standard solder alloy) was successfully applied in a surface mount PCB assembly performing as required in the screen printing and componentry placement while maintaining the excellent solderability consistent with the use of Reline as a solder flux.…”