Homoleptic complexes adopting octahedral coordination modes are usually less active in catalysis due to the saturated coordination around metal centers that prevents substrate activation in a catalytic event. In this work, we demonstrated that a homoleptic octahedral cobalt complex (1) of 4'-pyridyl-2,2';6',2''-terpyridine that experienced monoprotonation at the non-coordinating pyridyl moiety upon crystallization could serve as a highly efficient precatalyst for the hydroboration of styrene derivatives with Markovnikov selectivity. The solid-state structure of this precatalyst along with relevant homoleptic Co and Fe complexes has been characterized by X-ray crystallography.
View Article and Find Full Text PDFRegioselective epoxide ring-opening through hydroboration catalysed by a vanadium(III) dialkyl complex supported by a redox-active terpyridine ligand is reported. Secondary alcohols were obtained in high yields effective Markovnikov hydroboration of terminal epoxides, showcasing a new catalytic application of an earth-abundant vanadium(III) complex.
View Article and Find Full Text PDFSynthesis of branched "Markovnikov" alcohols is crucial to various chemical industries. The catalytic reduction of substituted epoxides under mild conditions is a highly attractive method for preparing such alcohols. Classical methods based on heterogeneous or homogeneous transition metal-catalyzed hydrogenation, hydroboration, or hydrosilylation usually suffer from poor selectivity, reverse regioselectivity, limited functional group compatibility, high cost, and/or low availability of the catalysts.
View Article and Find Full Text PDFA new diplumbane, namely [Pb(CHSiMe)], was synthesized and structurally characterized. This group 14 element compound was found to catalyse the hydroboration of ketones and aldehydes under mild conditions without the use of additives and solvents, leading to the synthesis of a range of alcohols in high yields after hydrolysis.
View Article and Find Full Text PDFReductive catalysis with earth-abundant metals is currently of increasing importance and shows potential in replacing precious metal catalysis. In this work, we revealed catalytic hydroboration and hydrosilylation of ketones and aldehydes achieved by a structurally defined manganese(ii) coordination polymer (CP) as a precatalyst under mild conditions. The manganese-catalysed methodology can be applied to a range of functionalized aldehydes and ketones with turnover numbers (TON) of up to 990.
View Article and Find Full Text PDFA novel nonanuclear copper(II) complex obtained by a facile one-pot self-assembly was found to catalyze the hydroboration of ketones and aldehydes with the absence of an activator under mild, solvent-free conditions. The catalyst is air- and moisture-stable, displaying high efficiency (1980 h turnover frequency, TOF) and chemoselectivity on aldehydes over ketones and ketones over imines. This represents a rare example of divalent copper catalyst for the hydroboration of carbonyls.
View Article and Find Full Text PDFHighly effective hydroboration precatalyst is developed based on a cobalt(II)-terpyridine coordination polymer (CP). The hydroboration of ketones, aldehydes, and imines with pinacolborane (HBpin) has been achieved using the recyclable CP catalyst in the presence of an air-stable activator. A wide range of substrates containing polar C═O or C═N bonds have been hydroborated selectively in excellent yields under ambient conditions.
View Article and Find Full Text PDFAn ionic cobalt-PNP complex is developed for the efficient α-alkylation of ketones with primary alcohols for the first time. A broad range of ketone and alcohol substrates were employed, leading to the isolation of alkylated ketones with yields up to 98%. The method was successfully applied to the greener synthesis of quinoline derivatives while using 2-aminobenzyl alcohol as an alkylating reagent.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2016
Well-defined manganese complexes based on inexpensive, readily available ligands, 2,2':6',2''-terpyridine and its derivatives have been prepared and employed for the selective hydroboration of alkenes, ketones and aldehydes. Highly Markovnikov regioselective hydroboration of styrenes as well as excellent chemoselective hydroboration of ketones over alkenes were achieved, for the first time, by an earth-abundant manganese catalyst.
View Article and Find Full Text PDFA mild and efficient synthesis of bicyclic oxazolidinones from quinols and isocyanates, under DBU-mediated conditions at room temperature, is described. The aza-Michael addition to substituted cyclohexadienones is stereoselective and chemoselective.
View Article and Find Full Text PDFActa Crystallogr Sect E Struct Rep Online
October 2008
In the mol-ecule of the title compound, C(8)H(11)N(7)S(2), the conformation about the N=N bond is trans and the thia-diazole rings are oriented at a dihedral angle of 2.92 (3)°. In the crystal structure, inter-molecular N-H⋯S hydrogen bonds link the mol-ecules into chains.
View Article and Find Full Text PDFActa Crystallogr Sect E Struct Rep Online
July 2008
In the title compound, C(28)H(28)N(4)O(4)S, the dihedral angles between the central thio-phene ring and its pendant oxadiazole rings are 1.2 (3) and 9.8 (3)°.
View Article and Find Full Text PDFIn the title compound, C(8)H(7)ClFNO, an intra-molecular C-H⋯O hydrogen bond forms a six-membered ring. In the crystal structure, mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds, forming infinite chains along the c axis.
View Article and Find Full Text PDFActa Crystallogr Sect E Struct Rep Online
May 2008
The molecule of the title compound, C(10)H(13)NO(3), is approximately planar. A network of N-H⋯O and weak C-H⋯O hydrogen bonds helps to consolidate the crystal structure.
View Article and Find Full Text PDFActa Crystallogr Sect E Struct Rep Online
April 2008
The title and the chemical diagram of the paper by Kang, Li, Zeng, Wang & Wang [Acta Cryst. (2007), E63, o4654] are corrected.[This corrects the article DOI: 10.
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