ChemInform Abstract: Percarboxylic Acid Oxidation of α‐Hydroxy‐Substituted Alkoxyallenes: The Unexpected Formation of Acyloxy‐Substituted 1,2‐Diketones and the Synthesis of Functionalized Quinoxalines.

Abstract

In addition to the transformation of the prepared 1,2‐diketones into quinoxalines, their conversion into imidazole, thiophene and 4‐oxoalk‐2‐enoate derivatives is described.

Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality

“…Nucleophilic attack of 3-chlorobenzoate would promote the ring opening of cationic intermediates 386 generating the observed diketones 382 after loss of methanol ( Scheme 66 ). 273 …”

“…Nucleophilic attack of 3-chlorobenzoate would promote the ring opening of cationic intermediates 386 generating the observed diketones 382 after loss of methanol (Scheme 66). 272 Enallenols, multifunctional molecular targets bearing an alkene and allene moieties along with a hydroxyl group, have Density functional theory calculations showed coincident results according to the experimental observations. Thus, in both gold-based alkenol (reaction profile from 393) and allenol (reaction profile from 394) cyclizations, protodemetalation was identified as the bottleneck step of the whole process, finding a much lower energy barrier for the allenol cyclization resulting in the formation of dihydrofuran 396 (Scheme 68, left).…”