Carbodiimides catalyse the reduction of CO2 with H-BBN or BH3·SMe2 to give either mixtures of CH2(OBBN)2 and CH3OBBN or (MeOBO)3 and B(OMe)3 under mild conditions (25-60 °C, 1 atm CO2). Stoichiometric reactions and theoretical calculations were performed to unveil the mechanism of these catalytic processes.
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http://dx.doi.org/10.1039/c8cc02139b | DOI Listing |
Org Lett
December 2024
Laboratory of Organic Synthesis and Catalysis, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand 247667, India.
We report the reactivity of in situ-generated nucleophilic siloxycarbenes from acylsilanes via the 1,2-Brook rearrangement in the presence of visible light with heterocumulenes. This method significantly advances from the conventional use of electrophilic carbenes stabilized by metal catalysts and harsh reaction conditions. The reactivity was explored with isocyanates, carbodiimides, and -sulfinylamines to synthesize α-ketoamides, hydantoins, oxoacetamidines, and amides.
View Article and Find Full Text PDFDalton Trans
November 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Homi Bhabha National Institute (HBNI), Bhubaneswar, 752050, India.
The low-valent germanium and tin hydrides, [LMH; L = {(ArHN)(ArN)-CN-C(NAr)(NHAr); Ar = 2,6-Et-CH}; M = Ge; (Ge-1), Sn (Sn-2)] bearing bis-guanidinato anions are employed as catalysts for chemoselective reduction of heterocumulenes hydroboration reactions. This protocol demonstrates that a wide range of carbodiimides (CDI), isocyanates, isothiocyanates, and isoselenocyanates undergo partial reduction, yielding the corresponding -boryl formamidine, -boryl formamide, -boryl thioformamide, and -boryl selenoformamide products, respectively. Isocyanates and isothiocyanates are further converted into -boryl methyl amines through hydrodeoxygenation (HDO) and hydrodesulfurization (HDS) reactions in the presence of catalyst Ge-1.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Department of Chemistry, School of Science, Institute of Science Tokyo, 2-12-1-E1-2 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
The molecular chemistry of metal-metal bonds is crucial for understanding the bonding and reactivity of metal-containing molecules as well as solid metals and their alloys, especially with respect to their application as catalysts for organic transformations and industrial processes. Despite the high efficiency of the recently developed nucleophilic alumanyl anions in the synthesis of diverse Al-metal bonds, the bonding between main group metals in a low oxidation state and the Al atom remains largely unexplored. This paper describes the reaction of an alumanyl anion with a chlorostannylene precursor to afford a compound with an unprecedented covalent Al-Sn bond.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Key Laboratory of Catalysis and Materials Sciences of the Ministry of Education, South-Central Minzu University, Wuhan, 430074, P. R. China.
Earth-abundant manganese oxides (MnO) were competitive candidates when screening catalysts for ammoxidation of alcohols into nitriles due to their redox property. However, over-oxidation and possible acid-catalyzed hydrolysis of nitriles into amides still limited the application of MnO in nitrile synthesis. In this work, manganese carbodiimide (MnNCN) was first reported to be robust for the ammoxidation of alcohols into nitriles, avoiding over-oxidation and the hydrolysis.
View Article and Find Full Text PDFJ Nanobiotechnology
September 2024
Institute for Experimental Molecular Imaging, RWTH Aachen University, 52074, Aachen, Germany.
Molecular ultrasound imaging with actively targeted microbubbles (MB) proved promising in preclinical studies but its clinical translation is limited. To achieve this, it is essential that the actively targeted MB can be produced with high batch-to-batch reproducibility with a controllable and defined number of binding ligands on the surface. In this regard, poly (n-butyl cyanoacrylate) (PBCA)-based polymeric MB have been used for US molecular imaging, however, ligand coupling was mostly done via hydrolysis and carbodiimide chemistry, which is a multi-step procedure with poor reproducibility and low MB yield.
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