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Please login to access the full content or check if you have access via9.13.1.5.1.3 Method 3: Hydroformylation and a Related Reaction of Propargylamines
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Black, D. StC., Science of Synthesis, (2001) 9, 466.
(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).
Meeeee 88 Meeeeeeee ee Meeeeeee eeee Meeeeeeeeeeeeee[888,888]
Meeeeeeeeeee Meeeeeeee
8-Meeeee-8M-eeeeeee (888):[888]
8-Meeeeeeeee-8-ee-8-eeeee (888; 8.88 e, 8.88 eeee) eee eeeeeee ee e eeeeeee eeeeeeeee eeee eeeeeeeee eeeeeeeeeeee (8.8 ee, 8.888 eeee), Me8M (8.88 ee, 8.888 eeee), MM eee M8 (88888 Meee) eee 88 e ee 88°M ee eeee 8-eeeeee-8M-eeeeeee (888) eeeee eeeeeeeeeee ee eee eeeeeeeee eeee eeeee; eeeee: 8.88 e (88%).
Meeee (8-Meeeee-8-eeeee-8-ee)-8M-eeeeeee-8-eeeeeeeeeee (888):[888]
M eeee ee 8.88 M MeMe ee Me8M (88 eM, 88 eeee) eee eeeee ee 8°M ee ee Me8M eeee ee eee-8-eee (8.8 eM, 88 eeee). Meeee 8.8 e, eee eeeeeeeee eeeeeee eee eeeee ee e eeeeeeeeee ee MeM (88.8 e, 88 eeee) ee Me8M (88 eM) ee 8°M eee eeeeeee eee 8.8 e. Mee eeeeeee eee eeeeee ee −88°M eee eeeeeee MeMe (88 eM, 88 eeee) eee eeeee. Meeee eeeeeeee eee eeeeeee ee 8°M ee eee eeeeee eeeee ee −88°M eee eee eeeee 888 (88.8 e, 88 eeee) eee eeeee, eeeeeeee eeeee 8 e ee 8-eeeeeeeeeeeeeee eeeeeeee (888; 8.8 eM, 88 eeee). Mee eeeeeee eee eeeeee eeeeee ee 88°M eee eeeee 88 e eee eeeee eeeeeee eee eeeeeeeeee eeee ee MM8Me eee eeeeeeeee eeee Me8M. Mee eeeeeee eeeee eee eeeeee eeee M8M, eeeee (Me8MM8), eeeeeeeeeeee, eee eee eeeeeee eeeeeeeeeeeeeee (eeeeeee eeeeeee, MM8Me8/Me8M 8:8) ee eeee eee eeeeeee 888; eeeee: 88.8 e (88%); ee 88°M.
References
[111] | Meeee, M. M.; Meeeee, M. M.; Meeeeee, M. M.; Meeeeee, M., Meee. M. Meee., (8888) 88, 8888. |
[112] | Meeeé, M. M.; Meeeee, M. M. M.; Meeee, M.; Meeeee, M. M. M.; Meeeeee, M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
[113] | Meeeee, M. M. M.; Meeee, M.; Meeee, M.; Meeeee, M. M. M.; Meeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |