Rearrangements, acyl-alkyl

The first step of the decarbonylation of acyl halides is their oxidative addition to form acylpalladium halides, which undergo acyl-alkyl rearrangement to form aryl- or alkylpal-ladium halides. Finally, elimination of j8-hydrogen affords alkenes and HCl. When j8-phenylpropionyl chloride was heated at 200 °C with Pd catalyst, styrene was formed as the main product, accompaiued by a small amount of l,5-diphenyl-l-penten-3-one. The... 

The acyl-alkyl rearrangement becomes a main path with some acyl halides. Actually, formation of the decarbonylation product has been reported in several cases as an abnormal reaction of the Rosenmund reduction. Sterically hindered acyl halides such as diphenylacetyl and triphenylacetyl chlorides and naphthoyl chloride undergo decarbonylation in attempted Rosenmund reduction (Scheme... 

Dimethylaminopyridine [1122-58-3] (DMAP) (24) has emerged as the preferred catalyst for a variety of synthetic transformations under mild conditions, particularly acylations, alkylations, silylations, esterifications, polymeri2ations, and rearrangements (100). POLYDMAP resin [1122-58-3], a polymeric version of DMAP, is available, and is as effective as DMAP as a catalyst for acylation reactions. Furthermore, it can be recycled without regeneration more than 20 times with very Htde loss in activity. POLYDMAP is a trademark of Reilly Industries, Inc. 

H-Azepin-2-one, 3-acetyl-synthesis, 7, 542-543 3/f-Azepin-2-one, 7-acetyl-synthesis, 7, 542-543 3H-Azepin-2-one, 3-acyl-rearrangements, 7, 505 3/f-Azepin-2-one, 3-acyl-2-alkoxy-formation, 7, 542-543 3H-Azepin-2-one, 1-alkyl-rearrangements, 7, 505 3/f-Azepin-2-one, N-alkyl-synthesis, 7, 511 Azepinones... 

Beckmann rearrangement, 4, 809 reactions, 4, 809 toxicity, 1, 136 Thiophene, 2-acyl-alkylation, 4, 777 synthesis, 4, 917 transacylations, 4, 760 Thiophene, 3-acyl-synthesis, 4, 918... 

Lateral chain modifications on QDO and PDO have been well documented in the literature. The described reactions have shown modifications in specific functional group—i.e., acylations, alkylations, decarboxylations, hydrolysis, rearrangements, substitutions—or the production of a new heterocycle, fusioned or not. Examples of the most recent descriptions are depicted in Fig. 6 [64-66],... 

Unlike acylation, alkylation of a primary or secondary 2- or 4-/6-aminopyrimidine usually takes place on a ring nitrogen to afford a 1-alkyl (92) or 3-alkyl iminopyrimidine, which subsequently may undergo a Dimroth rearrangement to its alkylamino isomer . 

This reaction is related to the Friedel-Crafts Alkylation, Darzens Olefin Acylation, Fries Rearrangement, Haworth Phenanthrene Synthesis, and Nencki Reaction. 

Biosynthesis of secondary metabolites involves numerous different mechanisms and reactions that are enzymatically catalyzed using several common mechanisms such as acylation, alkylation, decarboxylation, phosphorylation, hydride transfer, oxidation, elimination, reduction, condensation, rearrangement, and so on. The biosynthetic pathway may undergo changes due to natural causes (e.g., vimses or environmental changes) or unnatural causes (e.g., chemical or radiation) in an attempt to adapt or provide long life to the organism. 

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