The Lewis superacid, bis(1-methyl-ortho-carboranyl)borane, is rapidly accessed in two steps. It is a very effective hydroboration reagent capable of B-H addition to alkenes, alkynes, and cyclopropanes. To date, this is the first identified Lewis superacidic secondary borane and most reactive neutral hydroboration reagent.
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http://dx.doi.org/10.1002/anie.202307040 | 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 PDFInorg Chem
October 2024
Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China.
Three bis-formylfluorenimide ligands with different bridging groups were designed and synthesized, leading to the successful preparation of six novel alkylaluminum complexes through their reaction with alkylaluminum reagents (AlMe or AlEt). Complexes and were obtained by the reaction of 1,2-propylene-bridged diamine () with AlMe or AlEt. By reacting 1,2-cyclohexylene-bridged diamine () with AlMe or AlEt to obtain complexes and .
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, 730000, Lanzhou, P. R. China.
Skeletal editing of the core structure of heterocycles offers new opportunities for chemical construction and is a promising yet challenging research topic that has recently gained increasing interest. However, several limitations of the reported systems remain to be addressed. For example, the reagents employed are generally in high-energy, such as chlorocarbene precursors, nitrene species, and metal carbenes, which are also associated with low atomic efficiencies.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
CEA, IRAMIS, NIMBE, CNRS UMR 3299, 91191, Gif-sur-Yvette, France.
Hydroboranes are versatile reagents in synthetic chemistry, but their synthesis relies on energy-intensive processes. Herein, we report a new method for the preparation of hydroboranes from hydrogen and the corresponding haloboranes. Triethylamine (NEt) form with dialkylchloroboranes a Frustrated Lewis Pair (FLP) able to split H and afford the desired hydroborane with ammonium salts.
View Article and Find Full Text PDFSynlett
November 2023
UT Southwestern Medical Center, Department of Biochemistry, 5323 Harry Hines Blvd., Dallas Texas 75390-9038.
Rh-catalyzed asymmetric hydroboration of enol carbamates yields α-boryl carbamates in good enantioselectivity. The enol carbamate starting materials can be prepared with moderate selectivity using a modified Juila olefination and used as an mixture, taking advantage of the faster reactivity of the major isomer in the directed hydroboration. Optically active α-boryl carbamates participate in a Matteson-type homologation with Grignard reagents in which the O-carbamate is substituted with high conservation of optical activity to provide enantioenriched secondary boronic esters.
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