Search

A novel Ni0-catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents. [ABSTRACT FROM AUTHOR]

The mild, convenient and user-friendly process tolerates multiple functional groups. [ABSTRACT FROM AUTHOR]

An efficient ring opening of imidazoheterocycles induced by a direct C-H azidation resulting in an unusual formation of N-heterocyclic amides has been successfully developed through convergent paired electrolysis. A broad scope of pyridylbenzamides could be obtained in moderate to excellent yields under exogenous-oxidant, electrolyte- and metal-free electrochemical conditions. The methodology was transferred to continuous flow conditions resulting in notable improvements particularly in terms of cost-efficiency over traditional batch versions.

Here, we report the intramolecular Heck cross-coupling of 1,3-dienylphosphonates, affording unique and regioselective access to unprecedented benzofused phostone and phostam derivatives. The reactions proceeded under operationally simple and mild conditions with a wide substrate scope., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Nickel-catalyzed intramolecular hydrosilylation can be efficiently achieved with high regio- and stereoselectivities through two distinct methodologies. The first approach utilizes a conventional method, involving the reduction of nickel salt (NiBr 2 -2,2'-bipyridine) using manganese metal. The second method employs a one-step electrochemical reaction, utilizing the sacrificial anode process and NiBr 2 bipy catalysis. Both methods yield silylated heterocycles in good to high yields through a syn-exo-dig cyclization process. Control experiments and molecular electrochemistry (cyclic voltammetry) provided further insights into the reaction mechanism., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s-cis/s-trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction., (© 2021 Wiley-VCH GmbH.)

A catalytic intramolecular silapalladation of alkynes affords, in good yields and stereoselectively, syn-disilylated heterocycles of different chemical structure and size. When applied to silylethers, this reaction leads to vinylic silanols that undergo a rhodium-catalyzed addition to activated olefins, providing the oxa-Heck or oxa-Michael products, depending on the reaction conditions., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel Ni(0) -catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni(0) species is generated in situ by simply mixing the Ni(0) precatalyst [NiBr2 (bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbonickelations of alkynes and functionalization of the resulting vinylnickel moiety have been performed efficiently in a nickel-catalyzed domino cyclization-condensation process. This reaction, which does not require the preparation of any other organometallic reagent, proceeds only by exo-dig cyclization. This convenient and mild method constitutes a one-pot synthesis of substituted dihydrobenzofurans, chromans, isochromans, indoles, or indanes. Theses valuable products are generally obtained in good yields and high stereoselectivity. They are shown to be useful synthons for rapid access to functionalized polycyclic skeletons., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The mechanism of the intramolecular carbolithiation of lithiated propargylic ether 2 has been investigated both experimentally and theoretically. The results show that the action of one equivalent of n-butyllithium on 1 is sufficient to trigger halogen-lithium exchange and the subsequent heterocyclization step. Interestingly, the reaction stops at the stage of dihydrobenzofuran 6; no spontaneous elimination of lithium ethylate was observed. The fact that the E configuration of this adduct was exclusively produced suggests that the reaction proceeds by following an unprecedented anti addition on the alkyne. According to DFT calculations, this unexpected outcome is related to the intramolecular coordination of the lithium by one oxygen atom of the terminal acetal appendage: the O-Li interaction, which persists all along the ring-closure process, drives the cation to the E site of the final olefin. The calculations also show that in the absence of this coordination (as in conformers B and C of acetal 2), the Z olefin that results from a classical syn addition of the aryllithium should be obtained. The experiments were repeated with allene 1d. In this case, one equivalent of n-butyllithium suffices to trigger not only the exchange and the cyclization, but also the final elimination of lithium ethoxide. The DFT results indicate that the intramolecular addition of the original aryllithium on the central carbon atom of the allene 2b yields the expected benzofuran skeleton 3b, which bears a lithiated lateral chain at the 3-position. Both cyclizations go through low-lying transition states, as is expected for rapid reactions at low temperature.

[reaction: see text] Reformatsky-type reactions have been performed efficiently using an electroassisted iron-complex catalysis. Valuable product such as beta-hydroxyesters, ketones or nitriles are thus prepared with high yields.