We discovered a highly reactive λ3-hypervalent iodane species using an inorganic/organic base for the unorthodox synthesis of amides and ketoesters through grafting terminal alkynes. In contrast to the metal-catalyzed dehydrative approaches the in situ generated nonmetallic reagent efficiently created C-N/C-O and CO bonds with amines/alkynes and water at rt. This journal is © The Royal Society of Chemistry 2015.

DILIP MAITI

Chemistry

S KHAMARUI

R MAITI

University of Calcutta (informally known as Calcutta University or CU) is a collegiate public state university located in Kolkata, West Bengal, India.&nbsp;Within India it is recognized as a &quot;Five-Star University&quot; and accredited &quot;A&quot; Grade by National Assessment and Accreditation Council.

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The University of Calcutta has secured the Fifth position among the Universities of India in the prestigious &quot;Indian University Ranking 2019&quot; list, released by the NIRF of the Ministry of Human Resource Development, Government of India.

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It was established on 24 January 1857, and was one of the first institutions in Asia to be established as a multidisciplinary and Western-style university. Its alumni and faculty include several heads of state, heads of government, social reformers, prominent artists, only academy award winner and Dirac medal winner in India, many Fellows of the Royal Society and five Nobel laureates as of 2019 which is highest in South Asia.

University Of Calcutta

Chemical Communications

An expert and easy one-step catalytic method for the multi O-C coupling of alkyne is developed for the synthesis of valuable α-ketoesters and their chiral analogues, in contrast to the generation of esters by a noncatalytic method. The in situ generated powerful AgII catalyst from AgOTf is the workhorse in the oxidative grafting of alkyne with PhIO and alcohol. The radical mechanism is confirmed in our controlled experiments and UV-vis study. © 2015 American Chemical Society.

Organic Letters

In Situ Generated AgII-Catalyzed Selective Oxo-Esterification of Alkyne with Alcohol to Î±-Ketoester: Photophysical Study

An outstanding amidation/imidation process is demonstrated under metal-free benign reaction conditions by grafting terminal alkynes with varied amines and reactant cum solvent water. We explored diverse substrate scope in the nonconventional approach for synthesis of several classes of valuable compounds bearing amide linkages such as N-tosyl, N-aminotosyl, N-oxobenzyl, N-alkylated sugar-based secondary and tertiary chiral amides and also exploiting it for synthesis of valuable cyclic imides through simultaneous activation of triple bond and sp2C-H of aldehyde. The in situ-generated powerful reagent PhI(OH)2 enables selective cleavage and functionalization of terminal C-C triple bonds through simultaneous construction of C-N and C=O bonds. A measurable breakthrough in time-resolved ATR-MIR spectroscopy of the ongoing λ3-hypervalent iodine controlled reaction revealed formation of the unknown intermediates. The ATR-MIR technology is used for identifying infrared (IR) spectra of the individual intermediate/component present in the reaction mixture, which contains several compounds. The structures of the intermediates and their IR spectra were determined by DFT study. This unprecedented combination of experimental results and theoretical prediction provided useful information regarding the reaction insights such as the cleavage of triple bond, amination and amidation in the complex reaction process involving λ3-hypervalent iodine-bearing labile intermediates to the desired amide. The NMR and labelling (2H and 18O) studies supported the DFT-IR predicted reaction pathway. © The Royal Society of Chemistry 2015.

RSC Advances

Reactant cum solvent water: Generation of transient Î»3-hypervalent iodine, its reactivity, mechanism and broad application

Small Cu(0)-nanoparticles (NPs) are fabricated utilizing CuSO <inf>4</inf>·5H<inf>2</inf>O, surfactant (SDS) and ascorbic acid in aqueous medium. Its outstanding catalytic activity under low catalyst loading is developed toward reductive cleavage of isoxazoline, carbonyl azide and domino cyclization to furnish valuable 2-hydroxy-4-keto esters, primary amides and a new class of heterocycle, 4-hydroxy-2-pyrroline-5-one. © The Royal Society of Chemistry.

Green Chemistry

Cu(0) nanoparticle catalyzed efficient reductive cleavage of isoxazoline, carbonyl azide and domino cyclization in water medium

Intramolecular formal 1,3-dipolar cycloaddition of ketoimine is developed with PhIO for the first synthesis of fused-Δ1-pyrrolines. The scope of the reaction, complete diastereoselectivity and its rationalization by a computational study are reported. © 2011 The Royal Society of Chemistry.

First synthesis of fused-Î”1-pyrrolines via intramolecular 1,3-dipolar cycloaddition of ketoimine: A complete diastereoselective approach

Activation of π-bond with organic Lewis acid and cationic surfactant mediated direct transfer of halides to alkyne and alkene are demonstrated to afford α,α-dihaloketones and other valuable synthons with outstanding selectivities. © 2011 The Royal Society of Chemistry.

Addition of halide to Ï€-bond directly from aqueous NaX solution: A general strategy for installation of two different functional groups

(Chemical Equation Presented) A highly efficient strategy for chemoselective oxidation of aldoximes to nitrile oxides by iodosobenzene in neutral aqueous media is reported. Their in situ intermolecular 1,3-dipolar cycloaddition (1,3-DC) with olefins in nanometer aqueous micelles occurs with improved stereoselectivity and acceleration of reaction rate toward synthesis of new chiral synthons, 3-(2′-C-3′,4′,6′-tri-O- benzylglycal)-Δ2-isoxazolines and others. Construction of optically pure 2,8-dioxabicyclo[4.4.0]decene skeleta is performed by this green approach, and the stereochemistry of the new chiral center is predicted by B3LYP density functional theory. © 2008 American Chemical Society.

Journal of Organic Chemistry

Generation of nitrile oxides under nanometer micelles built in neutral aqueous media: Synthesis of novel glycal-based chiral synthons and optically pure 2,8-dioxabicyclo[4.4.0]decene core

Journal	Data powered by TypesetChemical Communications
Publisher	Data powered by TypesetRoyal Society of Chemistry
ISSN	1359-7345