52947-07-6Relevant articles and documents
Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes
Dale, Harvey J. A.,Nottingham, Chris,Poree, Carl,Lloyd-Jones, Guy C.
, p. 2097 - 2107 (2021)
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.
Purification method and preparation method of 13C methadoxetine
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Paragraph 0050-0053; 0059; 0063; 0067; 0071; 0075; 0079, (2020/06/20)
The invention relates to the technical field of purification of chemical drugs, in particular to a purification method and a preparation method of 13C methadoxetine. The purification method of 13C mexetine comprises the following steps: dissolving a 13C m
Trimethylsilyldiazo[13 c]methane: A versatile13 c-labelling reagent
Nottingham, Chris,Lloyd-Jones, Guy C.
, p. 374 - 402 (2019/08/20)
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