The synthesis of isoindolinones via copper-catalyzed sp(3) C-H functionalization of 2-alkyl-N-substituted benzamides is described. This process does not require the preparation of halogenated substitutes, expensive transition metals, or toxic Sn or CO gas. This method provides an efficient approach to generate various functionalized isoindolinones.
This paper describes
that an amide-base generated in situ from
tetramethylammonium fluoride (TMAF) and N(TMS)3 catalyzes
the deprotonative coupling of benzylic C(sp3)–H
bonds with carbonyls to form stilbenes. A variety of methylheteroarenes
(2-methylbenzothiophene, 2-methylbenzofuran, and 2-, 3-, or 4-methylpyridines)
are used as nucleophiles. Application to enamine synthesis using DMF
as an electrophile is also shown. The present system is effective
for toluenes (4-phenyl-, 4-bromo-, 2-bromo-, and 4-chlorotoluenes)
having low reactivity.
A method for the deprotonative silylation of aromatic C-H bonds has been developed using trifluoromethyltrimethylsilane (CFSiMe, Ruppert-Prakash reagent) and a catalytic amount of fluoride. In this reaction, CFSiMe is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-containing analogs of TAC-101, which is a bioactive synthetic retinoid with selective affinity for retinoic acid receptor α (RAR-α) binding. We also report further transformations of the silylated products into useful derivatives.
Herein,
we describe the first oxysilylation of unsaturated carboxylic
acids mediated by di-tert-butyl peroxide (DTBP),
which enables the rapid and efficient preparation of silyl lactone
compounds. This process tolerates functional groups, such as methyl,
methoxy, halogen (fluoride and chloride), and cyano moieties. Furthermore,
the strategy allows the application of a wide range of primary, secondary,
and tertiary hydrosilanes for functionalization.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.