(NHC)-Cu-catalyzed C(sp)-C(sp) bond formation has been successfully achieved under mild conditions. Nonactivated alkyl triflates, which could be easily derived from alcohols, were utilized as C-O electrophiles. Mechanistic studies suggested that copper acetylide was the active species. Scale-up reactions further demonstrated the practicality and efficiency of the developed strategy.
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http://dx.doi.org/10.1039/c7cc00891k | DOI Listing |
JACS Au
November 2024
Laboratory of Medicinal Chemical Biology, Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, 199 Ren'ai Road, Suzhou 215123, China.
(-)-Pleurotin () and (+)-dihydropleurotinic acid () are benzoquinone meroterpenoids isolated from fungal sources with powerful antitumor and antibiotic activities. Concise asymmetric total syntheses of the stereochemically pure (+)-dihydropleurotinic acid () and (-)-pleurotin () from the chiral pool ()-Roche ester-derived vinyl bromide have been achieved in 12 and 13 longest linear steps, respectively. The key transformations feature a Michael addition/alkylation cascade reaction to forge three contiguous stereocenters matched with the natural products, a PtO-catalyzed stereoselective reduction of olefin to generate the correct stereocenter at C3, a palladium-catalyzed Negishi cross-coupling between triflate and zinc reagent to introduce the redox-sensitive para-quinone moiety, and a hydroboration/copper-catalyzed carboxylation sequence to incorporate the vital carboxyl group.
View Article and Find Full Text PDFAcc Chem Res
November 2024
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China.
J Am Chem Soc
October 2024
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Decarboxylative cross-coupling of carboxylic acids and aryl halides has become a key transformation in organic synthesis to form C(sp)-C(sp) bonds. In this report, a base metal pairing between Fe and Ni has been developed with complementary reactivity to the well-established Ir and Ni metallaphotoredox reactions. Utilizing an inexpensive FeCl cocatalyst along with a pyridine carboxamidine Ni catalyst, a range of aryl iodides can be preferentially coupled to carboxylic acids over boronic acid esters, triflates, chlorides, and even bromides in high yields.
View Article and Find Full Text PDFInorg Chem
October 2024
LCM, CNRS, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, Palaiseau 91120, France.
This article focuses on the synthesis of heterobimetallic complexes of lanthanide and platinum. It describes the synthesis of the Cp*Yb(bipym)PtMe complex and its characterization, followed by its reactivity with oxidants, giving access to various Pt + IV compounds of trismethyl (PtMe) and tetramethyl (PtMe) fragments. Characterization of the electronic properties of the complexes by magnetic measurements demonstrated that the tetramethyl complex possesses a singlet ground state.
View Article and Find Full Text PDFChemistry
December 2024
Center for Molecular Materials, Inorganic Chemistry and Structural Chemistry Bielefeld University, Universitätsstraße 25, 33615, Bielefeld, Germany.
The alkylation of 3-/4-bromo- and -iodopyridine with methyl triflate smoothly affords the corresponding N-methylpyridinium triflate salts. An anion exchange with NaI or [PPh]Y (Y=Cl, Br, I) yields the corresponding halide salts. Most of them could be structurally characterized and their strong halogen bonds were investigated.
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