Hydroxylamines aminocarbonylation

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

A-Metal derivatives of A-(aUtoxycarbonyl) 0-(arenesulfonyl)hydroxylamines, [alkyl A-metal A-(arenesulfonyloxy)carbamates] 3i-o have been used in the amination of a-metallated carbonyl compounds to give A-Boc [N(COOBu-f)] or A-Alloc [N(COOCH2 CH=CH)] protected a-aminocarbonyl compounds. 

For stereoselective synthesis of a-aminocarbonyl compounds, a number of protocols have been reported using chiral enolates and A-(alkoxycarbonyl)-0-(arenesulfonyl) hydroxylamines. 

For stereoselective synthesis of a-aminocarbonyl compounds using 0-phosphinyl-hydroxylamines, a few procedures have been developed. Attempted amination of enolates of chiral alkyl 3-hydroxybutanoates with 0-(diphenylphosphinyl)hydroxylamine 4a or with its A,A-diisopropyl derivative 4d were found to be unsuccessful". ... 

Synonyms N-(Aminocarbonyl) hydroxylamine Carbamohydroxamic acid Carbamohydroximic... 

The first Mo(CO)6-promoted, microwave-assisted protocols for aminocarbonylation of aryl bromides and iodides to primary benzamides were presented in 2006 [34]. Hydroxylamine hydrochloride was used as a solid ammonia equivalent as it was found that hydroxylamine was smoothly reduced in situ by Mo(CO)6, generating free ammonia that could undergo the carbonylation. The conditions found suitable for this reaction included an aryl halide, Mo(CO)6, NH2OH HCI, 1,2, DBU, and DIEA in dioxane followed by 20 min of microwave heating at 110 °C for Ar-I and 150 °C for Ar-Br. Eight primary benzamides were synthesized from aryl bromides in 70-81% yield and the same amides from aryl iodides in 76-84% yield (Scheme 4.20). The method was also used in the synthesis of weak HIV-1 protease inhibitors (Scheme 4.21) [34]. 

Wu, X., Waimberg, J. and Larhed, M. (2006) Hydroxylamine as an ammonia equivalent in microwave-enhanced aminocarbonylations. Tetrahedron, 62, 4665-4670. 

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