Aluminum Catalyzed Selective Reduction of Heteroallenes via Hy-droboration: Amide/Thioamide/Selenoamide Bonds Construction and C=X (X= O, S, Se) Bond Activation DOI Creative Commons
Nabin Sarkar, Rajata Kumar Sahoo, Sharanappa Nembenna

et al.

Published: April 20, 2022

An unprecedented conjugated bis-guanidinate (CBG) stabilized aluminum dihydride, [LAlH2; (L = {(ArNH)(ArN)–C=N–C=(NAr)(NHAr)}; Ar 2,6- Et2-C6H3)] (I) catalyzed chemoselective hydroboration of heteroallenes such as carbodiimide (CDI)s, isocyanates, isothiocyanates, and isoselenocyanates is reported. A wide range heteroallenes, including electron-donating withdrawing groups, experience to obtain selectively N-boryl amide, N-borylaminal, methyl amine products. More importantly, a single sustainable molecular aluminum-based catalyst effectively catalyzes CDIs, into formamidines, formamides, thioformamides, selenoformamides, respectively. Fur-ther, heteroallene substrates undergo hydrodeoxygenation (HDO), hydrodesulfurization (HDS), hydrodeselenization (HDSe) reactions leading amines. In addition, series control kinetic experiments indicate that the hydride species are essential for all partial complete reduction steps breaking C=X (X O, S, Se) bonds in het-eroallenes.

Language: Английский

Radical hydroboration for the synthesis of organoboron compounds DOI
Yee Lin Phang, Ji‐Kang Jin, Feng‐Lian Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4275 - 4289

Published: Jan. 1, 2024

This review describes the recent research on radical hydroboration, which covers different boron sources including N-heterocyclic carbene borane, bis(pinacolato)diboron and pinacolborane, as well strategies in boryl generation.

Language: Английский

Citations

12
An air- and moisture-stable ruthenium precatalyst for diverse reactivity DOI Creative Commons
Gillian McArthur, Jamie H. Docherty, Mishra Deepak Hareram

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(7), P. 1141 - 1150

Published: April 3, 2024

Abstract Versatile, efficient and robust (pre)catalysts are pivotal in accelerating the discovery optimization of chemical reactions, shaping diverse synthetic fields such as cross-coupling, C–H functionalization polymer chemistry. Yet, their scarcity certain domains has hindered advancement adoption new applications. Here we present a highly reactive air- moisture-stable ruthenium precatalyst [( t BuCN) 5 Ru(H 2 O)](BF 4 ) , featuring key exchangeable water ligand. This versatile drives an array transformations, including late-stage C( sp )–H arylation, primary/secondary alkylation, methylation, hydrogen/deuterium exchange, 3 oxidation, alkene isomerization oxidative cleavage, consistently outperforming conventionally used (pre)catalysts. The generality applicability this is exemplified through potential for rapid screening photocatalytic reactions with suite situ generated photocatalysts containing hitherto unknown complexes, reactivities previously unreported ruthenium. observed suggestive generic platform reaction simplification accelerated that will enable broader accessibility to state-of-the-art catalysis.

Language: Английский

Citations

7
Unravelling a bench-stable zinc-amide compound as highly active multitasking catalyst for radical-mediated selective alk(en)ylation of unactivated carbocycles under mild conditions DOI Creative Commons

Sangita Sahoo,

Subarna Manna,

Arnab Rit

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(14), P. 5238 - 5247

Published: Jan. 1, 2024

The direct functionalization of unactivated organic moieties

Language: Английский

Citations

6
Visible-light-driven PhSSPh-catalysed regioselective hydroborylation of α,β-unsaturated carbonyl compounds with NHC-boranes DOI
Xinghua Liu,

Yujing Shen,

Cheng Lu

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(60), P. 8380 - 8383

Published: Jan. 1, 2022

A photo-induced transition-metal-free regioselective hydroborylation of α,β-unsaturated carbonyl compounds is developed. The PhSSPh reagent was employed as the photocatalyst, and NHC-BH3 used boron source. This transformation shows a broad substrate scope provides wide range α-borylcarbonyl molecules in good to excellent yields.

Language: Английский

Citations

20
Recent strategies and developments in the hydroboration of N-Heteroarenes mediated by transition and rare-earth metal complexes DOI

Priyanka Velmurugan,

Moris S. Eisen, Tapas Ghatak

et al.

Inorganica Chimica Acta, Journal Year: 2025, Volume and Issue: unknown, P. 122594 - 122594

Published: Feb. 1, 2025

Language: Английский

Citations

0
AgSbF6 Catalyzed Reduction of Nitroarenes by Phenylsilane to Anilines DOI
Priyabrata Biswal, Gobbilla Sai Kumar,

Vadapalli Chandrasekhar

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

AgSbF6-catalyzed activation of phenylsilane (PhSiH3) enables the efficient reduction nitroarenes to produce corresponding anilines. This methodology operates under additive-free conditions, making it highly efficient, scalable, and compatible with a wide range electronically diverse nitroarenes. The utility this method is exemplified by employing cheap, commercially available metal catalyst for facile synthesis various Furthermore, has been extended intermediates drug molecules, demonstrating its broad applicability.

Language: Английский

Citations

0
Coinage metal amido and thiolate SNS complexes: consequences of catalyst speciation in Cu(i)-catalysed carbonyl hydroboration DOI
Saeed Ataie, Maxwell I. Lohoar, Loïc P. Mangin

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(27), P. 4044 - 4046

Published: Jan. 1, 2023

Three new IPr-Ag- and -Au-SNS amido thiolate complexes were synthesized compared to their previously reported Cu analogues as carbonyl hydroboration catalysts (IPr = bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Although these showed no catalytic activity, treatment of the IPr-Ag-SNS complex with pinacolborane released N-borylated ligand, SMeNBpinSMe, (L1-Bpin). This finding led us reinvestigate IPr-Cu-SNS precatalyst, revealing that immediate loss L1-Bpin converts our catalyst system [CuH(IPr)]2.

Language: Английский

Citations

9
Against All Odds, Uranium and Thorium Iminato Complexes Enable the Cleavage of C═O Bonds in Isocyanates DOI

Konstantin Makarov,

Ida Ritacco, Natalia Fridman

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(17), P. 11798 - 11814

Published: Aug. 22, 2023

The catalytic activity of actinide-based catalysts is presented herein for the hydroboration and deoxygenation isocyanates with pinacolborane (HBpin). A modified class ligand systems possessing a five-membered ring core constructing N-heterocyclic iminato moiety introduced. All actinide complexes showed very good activities under mild conditions, low catalyst loadings achieving almost quantitative yields. wide number were studied including aliphatic isocyanates, aromatic diisocyanates yielding to corresponding borylated N-methyl amines formamides, which are easily hydrolyzed toward free formamides. These organoactinide exhibited great functional group tolerance methoxy, amido, halides. reaction selectivity was thoroughly investigated isocyanate functionality having double or triple unsaturated C–C bonds. Kinetic studies performed in order establish rate dependency on concentrations complex, HBpin, isocyanate. proposed mechanism based experiments affording more comprehensive understanding experimental trends reinforced by stoichiometric studies, thermodynamic measurements, deuterium-labeling experiments, theoretical DFT calculations.

Language: Английский

Citations

9
N-Heterocyclic carbene supported zinc catalysed N-formylation of diverse N–H functionalities with carbon dioxide under ambient conditions DOI

Sangita Sahoo,

Subarna Manna,

Arnab Rit

et al.

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(11), P. 3344 - 3350

Published: Jan. 1, 2023

A heteroditopic NHC ligand supported Zn-catalysed RT N -formylation of diverse N–H moieties with CO 2 (1 bar) using PhSiH 3 was developed, which offers excellent functional group tolerance, chemoselectivity, and synthons for biologically relevant compounds.

Language: Английский

Citations

8
Gallium Hydride‐Catalyzed Selective Hydroboration of Unsaturated Organic Substrates DOI
Sagrika Rajput, Rajata Kumar Sahoo, Nabin Sarkar

et al.

ChemPlusChem, Journal Year: 2024, Volume and Issue: 89(7)

Published: March 4, 2024

Abstract The first examples of tetrasubstituted conjugated bis‐guanidinate (CBG) supported monomeric and thermally stable gallium dihalides [LGaX 2 ], (X=Cl ( Ga−Cl ), I Ga−I )) dihydride Ga−H ) [LGaH ] (where L={(ArHN)(ArN)−C=N−C=(NAr)(NHAr)}; Ar=2,6‐Et −C 6 H 3 compounds are reported. reaction in situ generated LLi with 1.0 equiv. GaX (X=Cl, I) afforded . between Li[HBEt benzene yielded the compound All reported , were characterized by NMR, HRMS, single‐crystal X‐ray diffraction studies. was probed for hydroboration carbodiimides (CDI), isocyanates, isothiocyanates HBpin. Compound also found effective catalytic imines, nitriles, alkynes, esters, formates, affording corresponding products quantitative yields. Stoichiometric reactions a CDI performed to establish cycle.

Language: Английский

Citations

3