RESUMEN
A new electrochemical proton-coupled electron transfer method for the intermolecular CSP2-H amination of heteroarenes without oxidants, metal catalysts and external electrolytes has been developed. Various new N-containing heteroarenes were prepared in medium to high yields, and the indole-containing product could be converted into practical 2-oxindole by simple basic hydrolysis. Mechanistic investigation indicated that ester sulfonyl-substituted N-radicals could be formed by the combination of 2,6-lutidine and electrochemical oxidation, which is the key to achieve the desired chemoselectivity.
RESUMEN
A simple and efficient Pd-catalyzed oxidative cyclization system is developed for the chemo- and regioselective synthesis of 3,4-dihydro-benzothiadiazine 1,1-dioxides, which are formed through aminosulfonylation of ortho-iodoanilines with SO2. DABSO is utilized as the source of SO2, and the organic compound O2 acts as an oxidant. This direct C-S, S-N, and C-N functionalization is highly efficient, and broad functional group tolerance is observed, resulting in moderate to excellent yields of 3,4-dihydro-benzothiadiazine 1,1-dioxides. Furthermore, this method is amenable to gram-scale synthesis.
RESUMEN
A protocol was developed to construct five- to seven-membered cyclic nitrones through the gold-catalyzed 1,3-azaprotio transfer of allenyloximes under photoirradiation. The photoisomerization of oximes was suggested to convert the inert stereoisomer to a reactive one. This photodriven and gold-catalyzed ring formation could be further extended to the thermodynamically stable aryl ketoximes with an E-configuration, which previously displayed chemical inertness in the absence of light irradiation.
RESUMEN
A metal-free protocol for the direct construction of C(sp2)-N and C-O bonds via a PhI(OAc)2-mediated dehydrogenative aminoacyloxylation of ß,γ-unsaturated hydrazones with Togni reagent II is reported. Initiated by the carboxyl-containing species generated in situ from Togni reagent II, this method offers a new solution for regioselective functionalization at a remote site on ß,γ-unsaturated hydrazones, thus providing a straightforward method for the synthesis of acyloxyl-substituted pyridazines. This reaction features a broad substrate scope and mild conditions.
RESUMEN
An oxidative 6-endo-trig cyclization and [2 + 2] cycloaddition of ß,γ-unsaturated hydrazones/ketoximes and diazonium tetrafluoroborates for a synthetic strategy to pyridazin-4(1H)-ones/oxazin-4(1H)-ones under metal-free conditions is presented in a one-pot procedure. This protocol features excellent functional group tolerance and remarkable regioselectivity. A mechanistic study has been verified via 18O labeling and the H218O labeling method, in which O2 acts as both a reaction component and an oxidant.
RESUMEN
A direct arylsulfonylation of ß,γ-unsaturated hydrazones method, in which sulfonated pyrazolines are accessed by a three-component reaction of ß,γ-unsaturated hydrazones, DABSO, and aryldiazonium tetrafluoroborates, has been developed without external oxidants or catalysts. This transformation is triggered by the formation of arylsulfonyl radicals in situ from the reaction of aryldiazonium tetrafluoroborates and DABSO, and is enabled by controllable generation of C center radical, in which DABSO was utilized as the sulfone source and an oxidant in this radical-mediated cascaded reaction. A wide range of substrates can be applied in this process to afford pyrazolines in good yield, and it is amenable for gram-scale synthesis.
RESUMEN
A formal [4 + 2] cycloaddition of oximes with o-hydroxybenzyl alcohols was developed to easily synthesize diverse 1,3-benzoxazine derivatives. This synthesis was achieved under visible light-based organocatalytic and TsOH conditions. The reaction proceeds through the photoisomerization of oximes via visible light-mediated energy transfer, followed by the nucleophilic attack of o-QMs to oximes as a 1,2-dipole synthon, cyclization, and isomerization. The reaction exhibits a broad substrate scope and can be carried out under mild conditions. To demonstrate its synthetic usefulness, a gram-scale reaction was conducted, and the resulting 1,3-benzoxazine products were further transformed into other valuable compounds.
RESUMEN
Chemodivergent reactions of oximes and diazo esters involving Rh-catalyzed [3+2] annulation and photodriven O-H insertion have been developed to generate oxazoles and oxime ethers. A range of aldehyde and ketone oximes reacted with α-diazocarbonyl compounds in a controllable manner in which functional groups, including ketone, ester, amide, ether, thiol ether, silane, alkene, allene, and alkyne groups, were well tolerated.
RESUMEN
A copper(II)-catalyzed protocol to construct trans-configured ß-lactams and spirocyclic ß-lactams from oximes and methyl propiolate has been developed, which features excellent substrate flexibility and diastereoselectivity (up to >99:1 dr). In situ FT-IR mechanistic experiments support that ketene species might be involved in the formation of ß-lactams.
RESUMEN
A formal hydroxylation/cyclization of cyclopropanemethanols with DMSO is described, which involves isomerization and cyclization under Tf2O catalysis. This reaction undergoes ring-opening of the cyclopropane moiety to generate homoallylic alcohols, which react with DMSO to produce 3-benzylidenetetrahydrofurans. With various substituted groups on cyclopropanemethanols the reactions proceed smoothly and the desired 3-benzylidenetetrahydrofurans are obtained in moderate to good yields.
RESUMEN
A metal-free trifluorosulfonate anhydride (TFAA)-catalyzed strategy for the synthesis of spiro pyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and benzoquinones/ketones has been developed. With this general method, spiro pyrrolo[1,2-a]quinoxalines have been accessed via nucleophilic addition and cyclization. This reaction exhibits good functional group tolerance, and a wide range of products are obtained in moderate to good yields.
RESUMEN
A Cu-catalyzed method for the synthesis of 3,3'-bipyrroles from homopropargylic amines through tandem aerobic oxidative cyclization involving the formation of C-C bond has been developed. The features of this reaction are a small number of Cu catalysis and simple starting substrates. Moreover, this procedure exhibits good functional group tolerance and a series of 3,3'-bipyrroles derivatives are obtained in moderate to good yields.
RESUMEN
tert-Butyl nitrite promoted oxidative intermolecular sulfonamination of alkynes to synthesize substituted sulfonyl pyrroles from the alkynylamines and sulfinic acids via tandem addition/cyclization was developed. This reaction is performed well by employing tert-butyl nitrite as the oxidant, and various substituted sulfonyl pyrroles are formed in moderate to good yields with no requirement of metal catalysis.
RESUMEN
A straightforward Fe-catalyzed method for the synthesis of pyrrolo[1,2-a]quinoxalines from 1-(2-aminophenyl)pyrroles and cyclic ethers, which includes functionalization of C(sp3)-H bonds and the construction of C-C and C-N bonds, has been developed. The features of this reaction are Fe catalysis, low-cost and readily accessible starting materials. Moreover, this procedure exhibits good functional group tolerance and a series of pyrrolo[1,2-a]quinoxaline derivatives are obtained in moderate to good yields.