Direct Inter- and Intramolecular Addition of Amides to Arylalkenes Promoted by KOt-Bu/DMF

Abstract

Direct addition of tetrahydroisoquinoline derived amides to arylalkenes has been achieved in the presence of KOt-Bu/DMF. Both intermolecular and intramolecular reactions could occur in good yields. α-Amido alkyl radicals are proposed to be generated under the reaction conditions. The reaction is efficient for the synthesis of seven-membered nitrogen heterocycles. A homoprotoberberine was prepared conveniently via this method.

Modulation of Biorelevant Radical Reactions by Non‐covalent Interactions

“…After the initial H-atom abstraction, proteins undergo a series of structural modifications, including cross-linking, fragmentation, and loss of activity [59]. HAT from the C─H bonds of amines and amides is also a key step in the synthesis of substituted N-containing compounds under photoredox [61,62] or oxidative conditions [63,64]. For instance, the alkylation of dimethylformamide was achieved by radical oxidation using persulfate (S 2 O 8 2− ) in the presence of a visible light ruthenium-based catalyst (Scheme 20.19).…”

Intramolecular dehydrogenative coupling of biaryl tertiary amines promoted with t-BuOK/DMF: A convenient synthesis of 6-aryl-5,6-dihydrophenanthridines

“…[19][20][21][22][23][24][25] The formation of α-amino alkyl radicals or diphenylmethyl radicals initiated by t-BuOK/DMF was proposed. We speculated that α-amino alkyl radicals would also react with arenes which could provide a new entry to the preparation of polycyclic heterocyclic compounds, such as 5,6-dihydrophenanthridine derivatives.…”

Radical α,β-Dehydrogenation of Saturated Amides via α-Oxidation with TEMPO under Transition Metal-Free Conditions

“…Fortunately, the α-oxygenation of amides under radical pathways has been established by Maulide and Jiao et al. , The challenge is how to avoid enolization through the α-deprotonation by base. In previous work, t BuOK, a bulky strong base, has proven to be an efficient electron donor to initiate radical reactions . After carefully controlling the reaction conditions, we finally established a new method for the synthesis α,β-unsaturated amides from dehydrogenation of saturated amides.…”