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Photocatalytic α‐Tertiary Amine Synthesis via C−H Alkylation of Unmasked Primary Amines
Author(s) -
Ryder Alison S. H.,
Cunningham William B.,
Ballantyne George,
Mules Tom,
Kinsella Anna G.,
TurnerDore Jacob,
Alder Catherine M.,
Edwards Lee J.,
McKay Blandine S. J.,
Grayson Matthew N.,
Cresswell Alexander J.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202005294
Subject(s) - primary (astronomy) , tertiary amine , chemistry , catalysis , amine gas treating , azide , combinatorial chemistry , atom economy , photocatalysis , photoredox catalysis , organic synthesis , alkylation , organic chemistry , physics , astronomy
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 in situ 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 α‐tertiary amines, or their corresponding γ‐lactams. 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.