1272-44-2Relevant articles and documents
REACTION OF METALLOCENYL THIOKETONES WITH C5H5- AND - ANIONS. PREPARATION AND CRYSTAL STRUCTURES OF DIMERIC CYMANTRENYLPHENYLFULVENE DERIVATIVES
Batsanov, A. S.,Dolgova, S. P.,Bakhmutov, V. I.,Struchkov, Yu. T.,Setkina, V. N.,Kursanov, D. N.
, p. 341 - 354 (1985)
Ferrocenyl- and cymantrenyl-phenylthioketone react with C5H5- or - anions forming ferrocenyl- and cymantrenyl-phenylfulvene.The latter readily undergoes a Diels-Alder dimerization or a cycloaddition with a starting thioketone or analogous ketone.Crystal structures of two dimeric products were established.
Popp,Moynahan
, p. 454 (1969)
Synthesis of ferrocenyl thioketones and their reactions with diphenyldiazomethane
Mlostoń, Grzegorz,Hamera, Róza,Heimgartner, Heinz
, p. 2125 - 2133 (2015)
A series of ferrocenyl ketones were obtained via the Friedel-Crafts acylation with mixed anhydrides using ferrocene as a nucleophilic agent or ferrocene carboxylic acid as a precursor of the electrophilic species. The ketones obtained thereby undergo smooth thionation (tetrahydrofuran, 65°C) with Lawesson's reagent. The ferrocenyl thioketones react with diphenyldiazomethane via N2 elimination to afford the hitherto unknown ferrocenyl-substituted thiiranes.
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.
Highly Enantioselective Cobalt-Catalyzed Hydroboration of Diaryl Ketones
Liu, Wenbo,Guo, Jun,Xing, Shipei,Lu, Zhan
supporting information, p. 2532 - 2536 (2020/04/02)
A highly enantioselective cobalt-catalyzed hydroboration of diaryl ketones with pinacolborane was developed using chiral imidazole iminopyridine as a ligand to access chiral benzhydrols in good to excellent yields and ee. This protocol could be carried out in a gram scale under mild reaction conditions with good functional group tolerance. Chiral biologically active 3-substituted phthalide and (S)-neobenodine could be easily constructed through asymmetric hydroboration as a key step.
Hydrogen bond donor solvents enabled metal and halogen-free Friedel–Crafts acylations with virtually no waste stream
Liu, Guangchang,Xu, Bo
supporting information, p. 869 - 872 (2018/02/09)
We have developed a metal and halogen-free Friedel–Crafts acylation protocol with virtually no waste stream generation. We propose a hydrogen bonding donor solvent will form a hydrogen bonding network and may provide significant rate enhancement for Friedel–Crafts reactions. Trifluoroacetic acid is one of the strongest H-bond donor solvents, which is also volatile and can be easily recovered by distillation without need for reaction workup. Our protocol is a ‘green’ Friedel–Crafts acylation process: 1) the catalyst can be recovered and reused; 2) using halogen free starting material (carboxylic acids anhydride or carboxylic acids); 3) no need for aqueous reaction work-up; 4) minimum or no waste steam generation.
