Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI2/Amine/H2O under Mild Conditions

  • 10.1021/ja412578t
  • Journal of the American Chemical Society
  • p 2268-2271, Volume 136, Issue 6,
  • journal-article
Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI 2 /amine/H 2 O is reported. The reaction proceeds with C–N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C–O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the n X → π* C═O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C–N/C–O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.


Good but some limitations


Description of Study

Szostak and coworkers reported highly chemoselective reduction of amides ( primary, secondary, Tertiary) to alcohols using SmI2  /Amine /H2O under mild conditions.  They  reduced amide to alcohol by stirring amide (0.1mmol) with SmI2 ( 0.8 mmol),...