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9.13.1.5.1.3 Method 3: Hydroformylation and a Related Reaction of Propargylamines

DOI: 10.1055/sos-SD-009-00542

Black, D. StC.Science of Synthesis, (20019466.

(3-Arylpropargyl)amines undergo rhodium-catalyzed hydroformylation to give 3- (or 4-) arylpyrroles in very high yield. Relatively poor yields are obtained from the related alkylpropargylamines, and this, together with the requirement for autoclave conditions, rather restricts the synthetic utility of the method. A good example is the conversion of 3-phenylprop-2-yn-1-amine (162) into 3-phenyl-1H-pyrrole (164) via the intermediate 163 (Scheme 26).[‌111‌] A related process makes use of the formation of organocopper derivatives from N-silylated 4-aminobut-2-ynoates. Although the yields are modest, a major advantage of this methodology is the insertion of the C1 unit as an acyl halide, which offers great versatility.[‌112‌,‌113‌] Thus, the propargylamine derivative 165 is converted by reaction with a lithium methyl cuprate into the organocopper intermediate 166, which combines with 2-thienylcarbonyl chloride (167) to give the thienylpyrrole 168 (Scheme 26).

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