Abstract
Manganese(III)-catalyzed formal [3+2] annnulation
of vinyl azides and β-keto acids has been developed for
the synthesis of substituted NH pyrroles with a wide range of substituents.
Key words
manganese(III) catalysts - radical reactions - vinyl azides - β-keto acids - pyrroles
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General Procedure
for Mn(acac)
3
-Catalyzed Pyrrole Formation from Vinyl Azides
and β-Keto Acids: To a solution of α-azido
styrene (1a; 52.8 mg, 0.364 mmol) and 2-oxocyclohexanecarboxylic
acid (2a; 155.2 mg, 1.09 mmol) in DMF (3.6
mL) was added Mn(acac)3 (12.8 mg, 0.0364 mmol) and the
mixture was stirred for 5 h. The reaction mixture was quenched with
a pH 9 ammonium buffer, and then extracted with Et2O
(2 ×). The combined organic extracts were washed with brine,
dried over MgSO4 and concentrated. Purification of the
crude product by flash column chromatography (florisil; hexane-EtOAc = 97:3) afforded
3aa (59.5 mg, 0.302 mmol) in 83% yield.
