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. Author manuscript; available in PMC: 2024 Feb 15.
Published in final edited form as: J Am Chem Soc. 2023 Feb 1;145(6):3294–3300. doi: 10.1021/jacs.2c12767

Table 2.

Selective N-Demethylation over N-Debenzylation via Steric Control of C(sp2)-Bromidesa,c

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a

Reactions were run on a 0.2 mmol scale at ambient temperature in MeCN (0.1 M) using 5CzBN (1 mol%), Ni (5 mol%), dtbbpy (8 mol%), C(sp2)-Br (1.1-1.5 equiv), NaOPiv (1 equiv) and H2O (36 μL) under 8-30 h of blue LEDs irradiation (427 nm) until complete conversion of the amine substrate. Yields of secondary amines and ratios were determined by GC-MS with 1,3,5-trimethoxybenzene as standard. Yields in parentheses refer to isolated amine products after subsequent one-pot Boc protection with NEt3 and Boc2O.

b

Br2 and Ni(cod)2 was used.

c

Trace side products such as primary amine and imine were observed as a result of over-oxidation, along with unreacted substrate. Driving the reaction to completion also results in overoxidation by-products.