116332-61-7Relevant articles and documents
Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines
Gim, Hyo Jin,Jung, Michael E.
, p. 2548 - 2552 (2019)
Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N -methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.
Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes
Dale, Harvey J. A.,Nottingham, Chris,Poree, Carl,Lloyd-Jones, Guy C.
supporting information, p. 2097 - 2107 (2021/02/01)
Alkylidene carbenes undergo rapid inter- and intramolecular reactions and rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility of alkylidene carbene intermediates, yet prior efforts to categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes of carbene generation, ultrashort carbene lifetimes, mechanistic ambiguities, and the need to individually prepare a series of 13C-labeled precursors. Herein we report on the rearrangement of 13C-alkylidene carbenes generated in situ by the homologation of carbonyl compounds with [13C]-Li-TMS-diazomethane, an approach that obviates the need for isotopically labeled substrates and has expedited a systematic investigation (13C{1H} NMR, DLPNO-CCSD(T)) of migratory aptitudes in an unprecedented range of more than 30 alkylidene carbenes. Hammett analyses of the reactions of 26 differentially substituted benzophenones reveal several counterintuitive features of 1,2-migration in alkylidene carbenes that may prove of utility in the study and synthetic application of unsaturated carbenes more generally.
Saturated Bioisosteres of ortho-Substituted Benzenes
Denisenko, Aleksandr,Garbuz, Pavel,Mykhailiuk, Pavel K.,Shishkina, Svetlana V.,Voloshchuk, Nataliya M.
supporting information, p. 20515 - 20521 (2020/08/21)
Saturated bioisosteres of ortho-disubstituted benzenes (bicyclo[2.1.1]hexanes) were synthesized, characterized and validated. These cores were incorporated into the bioactive compounds Valsartan, Boskalid and Fluxapyroxad instead of the benzene ring. The