 highly chemoselective 
 direct reduction of primary , secondary , and 
 tertiary amides to alcohols using smi2/amine / h2o 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 nx  
 *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 . 
Supplementary Material