Flourishing reactivities of isocyanates and isothiocyanates using group 13 elements DOI Creative Commons

Sanjukta Pahar,

Aleksandra Górecka,

Emma Richards

et al.

Cell Reports Physical Science, Journal Year: 2023, Volume and Issue: 4(12), P. 101745 - 101745

Published: Dec. 1, 2023

Due to the upswing in interest development of efficient hydroelementation reactions construct C–heteroatom bonds either stoichiometrically or catalytically, activation isocyanates and isothiocyanates has received recent attention. The derivatization using earth-abundant inexpensive group 13 main-group compounds have lately been observed more frequently. In this review, we aim highlight C=N vs. C=O C=S bonds, scope cycloaddition iso(thio)cyanates with compounds, findings frustrated Lewis pairs (FLPs). addition, hydroboration hydroamination these substrates are also discussed formulate synthetically important urea/amide thioamide derivatives.

Language: Английский

Neutral Cyclic Nitreones: Electronic Structure Analysis Reveals an Unorthodox Perspective of Several Zwitterionic Heterocyclic Species DOI
Astha Gupta,

Pooja Saulanki,

Prasad V. Bharatam

et al.

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

Published: March 10, 2025

Nitreones are compounds with the general formula L → N+ ← L'. These exhibit medicinal properties and have found applications in phase transfer catalysis. A few nitreones cyclic; protonated cycloguanil (an antimalarial agent) is most prominent example. Recently, a more cyclic were experimentally reported, which central was shown to nitreone character. This led attention being paid chemistry of neutral nitreones. thorough literature search two sets nitreones: C N type P type. In this work, we report quantum chemical analysis exploring electronic structure Molecular orbital analysis, electron density charge, localization function (ELF), complexation energy values, Tolman parameter (TEP) all indicate that studied do carry nitrogen N(I) oxidation state lone pairs at nitrogen; thus, they qualify be considered as

Language: Английский

Citations

0
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
NHC-Silyliumylidene Cation-Catalyzed Hydroboration of Isocyanates with Pinacolborane DOI

Yeow-Chuan Teo,

Dexter Loh,

Bi‐Xiang Leong

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(41), P. 16867 - 16873

Published: Oct. 4, 2023

The low-oxidation-state silicon-catalyzed hydroboration of isocyanates with pinacolborane (HBpin) using the NHC-silyliumylidene cation catalyst [(IMe)2SiH]I (1, IMe = :C{N(Me)C(Me)}2) is described. In catalysis, Si lone pair electrons activate isocyanates, and latter react HBpin to form N-boryl formamides at room temperature. Catalyst 1 further activates 70 °C, intermediates which methylamines (pinB)2O.

Language: Английский

Citations

6
Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide DOI
Tatyana S. Koptseva,

Alexandra A. Skatova,

Mikhail V. Moskalev

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(10), P. 4643 - 4651

Published: Jan. 1, 2024

This work demonstrates various ways of binding and transformation heteroallenes by acenaphthenediimine aluminum oxide.

Language: Английский

Citations

2
Mixed Lithium–Aluminum Hydrides Bearing Ar-Bian Ligands: Reactivity Toward Heteroallenes DOI
Tatyana S. Koptseva,

Andrey A. Bazanov,

Alexandra A. Skatova

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(13), P. 1438 - 1446

Published: June 13, 2024

The reactivity of [(dpp-Bian)Al(H)2Li(THF)3] (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) and [(ArBIG-Bian)Al(H)2Li(THF)4] (2) (ArBIG-Bian 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) toward isocyanates carbodiimides has been investigated. A treatment 1 with tert-buthylisocyanate affords the formimidate derivative [(dpp-Bian)Al(μ2-OC(H)NtBu)2Li(THF)] (3). related [(ArBIG-Bian)Al(μ2-OC(H)NCy)2Li(THF)] (4) [(ArBIG-Bian)Al((μ-OC(H)NPh)Li(THF)3)(OC(H)NPh)] (5) have obtained by reacting 2 cyclohexyl phenylisocyanates, respectively. Cyclohexylcarbodiimide reacts to give corresponding amidinate derivatives [(dpp-Bian)Al(CyNC(H)NCy)(μ-CyNC(H)NCy)Li(THF)2] (6) [(ArBIG-Bian)Al(CyNC(H)NCy)][Li(DME)3] (7). Complexes 3-7 were characterized IR NMR spectroscopy. molecular structures compounds determined single-crystal X-ray analysis. Both serve well as catalysts in hydroboration pinacolborane (HBpin).

Language: Английский

Citations

2
Carbodiimide and Isocyanate Hydroboration by a Cyclic Carbodiphosphorane Catalyst** DOI Creative Commons

Ben A. Janda,

Julie Tran,

Daniel K. Chang

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(3)

Published: Oct. 17, 2023

Abstract We report hydroboration of carbodiimide and isocyanate substrates catalyzed by a cyclic carbodiphosphorane catalyst. The outperformed the other Lewis basic carbon species tested, including zerovalent compounds, phosphorus ylides, an N ‐heterocyclic carbene, olefin. Hydroborations seven carbodiimides nine isocyanates were performed at room temperature to form ‐boryl formamidine formamide products. Intermolecular competition experiments demonstrated selective alkyl over ketone substrates. DFT calculations support proposed mechanism involving activation pinacolborane catalyst, followed hydride transfer B−N bond formation.

Language: Английский

Citations

5
Chemoselective Luche-type reduction of α,β-unsaturated ketones by aluminium hydride catalysis DOI

Ben Yan,

Xiaoli Ma,

Ziyuan Pang

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(9), P. 4127 - 4131

Published: Jan. 1, 2024

Herein, we describe a greener and more general method for the chemoselective reduction of α,β-unsaturated ketones using organoaluminum catalysis.

Language: Английский

Citations

0
Low-Valent Germanium and Tin Hydrides as Catalysts for Hydroboration, Hydrodeoxygenation (HDO), and Hydrodesulfurization (HDS) of Heterocumulenes DOI
Sayantan Mukhopadhyay, Rajata Kumar Sahoo,

A. Ganesh Patro

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(45), P. 18207 - 18216

Published: Jan. 1, 2024

The low-valent germanium and tin hydrides, [LMH; L = {(ArHN)(ArN)-CN-C(NAr)(NHAr); Ar 2,6-Et

Language: Английский

Citations

0
Flourishing reactivities of isocyanates and isothiocyanates using group 13 elements DOI Creative Commons

Sanjukta Pahar,

Aleksandra Górecka,

Emma Richards

et al.

Cell Reports Physical Science, Journal Year: 2023, Volume and Issue: 4(12), P. 101745 - 101745

Published: Dec. 1, 2023

Due to the upswing in interest development of efficient hydroelementation reactions construct C–heteroatom bonds either stoichiometrically or catalytically, activation isocyanates and isothiocyanates has received recent attention. The derivatization using earth-abundant inexpensive group 13 main-group compounds have lately been observed more frequently. In this review, we aim highlight C=N vs. C=O C=S bonds, scope cycloaddition iso(thio)cyanates with compounds, findings frustrated Lewis pairs (FLPs). addition, hydroboration hydroamination these substrates are also discussed formulate synthetically important urea/amide thioamide derivatives.

Language: Английский

Citations

0