Amidation, carbonylative

Fmoc derivative (Section 26.7) A fluorenylmethyloxy-carbonyl amide-protected amino acid. 

Boat conformation (cyclohexane), steric strain in, 118 Boc (fcJrf-butox carbonyl amide). 

Reaction of /3-carbonyl amides with the Lawesson s reagent under microwave irradiation gave thiazoles in acceptable yields [37]. The reaction was the same one previously reviewed for the synthesis of thiophenes and was also employed for the preparation of thiadiazoles (Scheme 10, X = NH, Y = CH). 

M-NHC catalysts in this area. Metal catalysed carbonylation also provides an alternative synthetic ronte to the prodnction of materials that traditionally reqnire highly toxic precnrsors, like phosgene. This section discnsses carbonylation of aryl hahdes, oxidative carbonylation of phenolic and amino componnds, carbonylation of aryl diazoninm ions, alcohol carbonylation, carbonylative amidation, and copolymerisation of ethylene and CO. 

Step 3. Nucleophilic Attack by Oxygen or Nitrogen on Carbonyl Amide... 

The amide II band is not present in the spectra of lactams. As in the case of cyclic ketones, however, the carbonyl (amide I) band shifts to higher frequency as the size of the ring decreases. 

Amides can behave as a weak acid or a weak base. They are less basic than amines due to the electron withdrawing properties of the carbonyl- Amides are hydrolysed by either strong acids or strong bases. 

The resistance to cleavage is an indication of the superelectrophilic character of dication 150c. Several aromatic compounds have likewise been shown to produce dicationic species upon the protonation of carboxyl and carbonyl functional groups. Other bis-carboxonium dications have been described involving protonation of carbonyl, amide, and other groups.50 These distonic superelectrophiles (152-153) have been shown to be useful in condensation reactions (eqs 52-53). 

Scheme 17 Pd(OAc)2/SIPr HCl-catalyzed carbonylative amide formation...

Phosphorsaure-alkoxy carbonyl-amid (b2w. -anilinocarbonylamid)-alkyl-ester konnen in Ausbeuten von 87-93% in einer Eintopfreaktion ausgehend von Phosphorsaure-dichlorid-isocyanaten gewonnen werden153. 

Aus Thiophosphorsaure-0,0-diester-isocyanaten werden mit Alkoholen bzw. Alkan-thiolen (207Diethylether) Thiophosphorsaure-alkoxycarbonylamid- bzw. -(alkyl-thio-carbonyl)-amid-0,0-diester (80—99%) erhalten433 ... 

Thiophosphorsaure-bis-[alkoxycarbonyl- (bzw. aminocarbonyl-, aminoxy-carbonyl) -amid]- O-ester... 

Complexes 132 and 133 reacted with a range of unsaturated substrates to afford [2 + 2] cycloaddition products. Addition of carbon dioxide to 133 gave complex 145 as adjudged by FTIR spectroscopy, mass spectrometry, and combustion analysis. Complexes 133 and 132 afforded complexes 146 and 147, respectively, after addition of adamantyl isocyanate. The formation of 146 and 147 is noteworthy from a regioselective point of view in that 1,2-addition gives the carbonyl-amide product. However, the alkoxide-imine product might have been expected given that the Lewis acidity of... 

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