US EPA

1453318 

Journal Article 

Hypervalent Iodine Catalyzed Hofmann Rearrangement of Carboxamides Using Oxone as Terminal Oxidant 

Yoshimura, A; Middleton, KR; Luedtke, MW; Zhu, C; Zhdankin, VV 

2012 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

77 

24 

11399-11404 

English 

23176018 

10.1021/jo302375m 

WOS:000312564900047 

Hofmann rearrangement of carboxamides to carbamates using Ozone as an oxidant can be efficiently catalyzed by iodobenzene. This reaction involves hypervalent iodine species generated in situ from catalytic amount of PhI and Oxone in the presence of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) in aqueous methanol solutions. Under these conditions, Hofmann rearrangement of various carboxamides affords corresponding carbamates in high yields. 

Aqueous methanol solutions; Carboxamides; Catalytic amounts; High yield; Hofmann rearrangement; Hypervalent iodine; Iodobenzene; Terminal oxidants; Catalysis; Organic compounds; Oxidants; Iodine; 1,1,1,3,3,3 hexafluoroisopropanol; 2 (2 chlorophenyl)acetamide; 2 (3 chlorophenyl)acetamide; 2 (4 bromophenyl)acetamide; 2 (4 chlorophenyl)acetamide; 2 (4 fluorophenyl)acetamide; 2 [(4 trifluoromethyl)phenyl]acetamide; 2 methylhexanamide; 2,2 dimethylhexanamide; 5 phenylpentanamide; 6 phenylhexanamide; 7 bromoheptanamide; 7 chloroheptanamide; amide; bicyclo[2.2.1]heptane 2 carboxamide; carbamic acid; cyclopentanecarboxamide; iodine; iodobenzene; methanol; methyl n (2 chlorobenzyl)carbamate; methyl n (3 chlorobenzyl)carbamate; methyl n (4 bromobenzyl)carbamate; methyl n (4 chlorobenzyl)carbamate; methyl n (4 fluorobenzyl)carbamate; methyl n (4 methylbenzyl)carbamate; methyl n benzylcarbamate; octanamide; propanol; sodium peroxide; unclassified drug; aqueous solution; article; catalysis; chemical modification; chemical structure; Hoffmann rearrangement; ligand binding; proton nuclear magnetic resonance; stereochemistry; stoichiometry; substitution reaction