The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions
نویسندگان
چکیده
N-acyliminium ions are useful reactive synthetic intermediates in a variety of important carbon-carbon bond forming and cyclisation strategies in organic chemistry. The advent of an electrochemical anodic oxidation of unfunctionalised amides, more commonly known as the Shono oxidation, has provided a complementary route to the C-H activation of low reactivity intermediates. In this article, containing over 100 references, we highlight the development of the Shono-type oxidations from the original direct electrolysis methods, to the use of electroauxiliaries before arriving at indirect electrolysis methodologies. We also highlight new technologies and techniques applied to this area of electrosynthesis. We conclude with the use of this electrosynthetic approach to challenging syntheses of natural products and other complex structures for biological evaluation discussing recent technological developments in electroorganic techniques and future directions.
منابع مشابه
Highly enantioselective introduction of bis(alkoxycarbonyl)methyl group into the 2-position of piperidine skeleton
Copper ion catalyzed carbon-carbon bond forming reaction of N-acyliminium ions with diaryl malonates was achieved with high enantioselectivity. The key intermediates in the method were 2-methoxy-3,4-didehydropiperidines, which were easily prepared through electrochemical oxidation of 1-(p-methoxybenzoyl)piperidine in methanol followed by the conversion of the oxidation product to didehydropiper...
متن کاملElectrochemical oxidation of amides of type Ph2CHCONHAr.
Anodic oxidation of N-aryl-2,2-diphenylacetamides in acetonitrile undergoes three types of bond-cleavage, one between the benzylic carbon and the carbonyl group, the second between a carbonyl and 'N', and the third between the 'N' atom and aryl group. The selectivity of the cleavage and nature of emerged products is highly dependent on the nature of substituent attached to the aryl group. For e...
متن کاملA facile synthesis of pyrrolo-(di)-benzazocinones via an intramolecular N-acyliminium ion cyclisation.
A facile, moderate to high yielding synthesis of hexahydro-(di)-benzazocinones is described via an intramolecular N-acyliminium ion cyclisation. The iminium ion intermediates are formed from the readily available 4,4-diethoxybutyl amides with an excess of triflic acid. For electron-withdrawing substituents, better yields were obtained from the pre-formed 2-hydroxypyrrolidine amides. From NMR st...
متن کاملA new paradigm for carbon-carbon bond formation: aerobic, copper-templated cross-coupling.
Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 degrees C at neutral pH using thiol esters derived from bulky 2 degrees amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically ...
متن کاملPlatinum Nanoparticles Deposited on Oxygen-Containing Functional Groups at Carbon Vulcane XC-72 as a Cathode Catalyst for Direct Methanol Fuel Cell
Surface oxidized carbon vulcane XC-72 is prepared as catalyst support and platinumnanoparticles are chemically anchored onto the modified surface. The nanoparticles of Pt weresynthesized by reduction of H2PtCl6 with sodium borohydride in a 5.5 M buffer solution ofsodium citrate; the complexation of citrate with metal ions is beneficial to the formation ofnanoparticles. The electro-oxidation of ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
دوره 10 شماره
صفحات -
تاریخ انتشار 2014