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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/20889
Title: Indium promoted C(sp3)-P bond formation by the Domino A3-coupling method-a combined experimental and computational study
Authors: Das S.
Rawal P.
Bhattacharjee J.
Devadkar A.
Pal K.
Gupta, Puneet
Panda T.K.
Published in: Inorganic Chemistry Frontiers
Abstract: A highly efficient and green process for the synthesis of α-aminophosphonates has been developed through a one-pot three-component reaction of various aldehydes, amines, and phosphine oxide in the presence of indium complexes as competent catalysts under neat conditions at room temperature. The indium complexes [κ2-{RNC(Me)CHC(Me)O}2InCl] (R = 2,6-diisopropylphenyl (Dipp), 2a; 2,4,6-trimethylphenyl (Mes), 2b), and [κ2-{DippNC(Me)CHC(Me)O}2In(OTf)] [(OTf = CF3SO3-, 3a) were synthesised by the reaction of protic ligand β-ketoimine with an equivalent amount of lithium hexamethyldisilazide followed by the addition of indium trichloride in toluene. The solid-state structures of complexes 2a, 2b, and 3a are established by single-crystal X-ray diffraction analysis. In all the indium complexes, the indium ion is five-fold coordinated and adopts a distorted trigonal bipyramidal geometry around it. The catalytic method offers an efficient approach with a broad range of α-aminophosphine oxide derivatives in excellent yields with good functional group tolerance. Density functional theory based mechanistic studies demonstrate energetically affordable pathways at room temperature for the indium catalysed aminophosphorylation of benzaldehyde, phenylamine, and diphenylphosphine oxide. The rate-limiting step deduced in this aminophosphorylation is the initial step in which phenylamine reacts with indium-coordinated benzaldehyde to build a C-N bond with a concomitant transfer of a proton from phenylamine to benzaldehyde. © the Partner Organisations.
Citation: Inorganic Chemistry Frontiers, 8(5): 1142-1153
URI: https://doi.org/10.1039/d0qi01210f
http://repository.iitr.ac.in/handle/123456789/20889
Issue Date: 2021
Publisher: Royal Society of Chemistry
Keywords: Aniline
Chemical bonds
Computation theory
Coordination reactions
Density functional theory
Phosphorus compounds
Single crystals
Synthesis (chemical)
X ray powder diffraction
Computational studies
Diphenylphosphine oxides
Distorted trigonal bipyramidal geometries
Lithium hexamethyldisilazide
Rate-limiting steps
Single crystal X-ray diffraction analysis
Solid-state structures
Three component reactions
Lithium compounds
ISSN: 20521553
Author Scopus IDs: 57213459748
57217096933
56097234400
57217388607
7005269790
57215231630
7006104344
Author Affiliations: Das, S., Department of Chemistry, Indian Institute of Technology Hyderabad Kandi, Sangareddy Telangana, 502285, India
Rawal, P., Computational Catalysis Center, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, 247667, India
Bhattacharjee, J., Department of Chemistry, Indian Institute of Technology Hyderabad Kandi, Sangareddy Telangana, 502285, India
Devadkar, A., Department of Chemistry, Indian Institute of Technology Hyderabad Kandi, Sangareddy Telangana, 502285, India
Pal, K., Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata, 700009, India
Gupta, P., Computational Catalysis Center, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, 247667, India
Panda, T.K., Department of Chemistry, Indian Institute of Technology Hyderabad Kandi, Sangareddy Telangana, 502285, India
Corresponding Author: Panda, T.K.; Department of Chemistry, India; email: tpanda@chy.iith.ac.in Gupta, P.; Computational Catalysis Center, India; email: puneet.gupta@cy.iitr.ac.in
Appears in Collections:Journal Publications [CY]

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