Anup Bhunia

• M.Sc
• PostDoc Position at University of Münster

An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET) with a reaction partner. The known concept of consecutive photoinduced electron transfer (con‐PET) leads to catalytically active species even higher in energy by the...

An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET) with a reaction partner. The known concept of consecutive photoinduced electron transfer (con‐PET) leads to catalytically active species even higher in energy by the...

An extended class of organic multi‐redox systems was derived from bicyclic(alkyl)amino carbenes (BICAACs). The highly‐conjugated system undergoes a total of 4 redox events spanning a 1.8 V redox range. These organic compounds exhibited four different stable redox states (dication, radical cation, neutral and radical anion), and all of them were cha...

Single electron redox processes allow the formation of highly reactive radicals – valuable intermediates that enable unique transformations in organic chemistry (1,2). An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET...

Solid-state radical generation is an attractive but underutilized methodology in the catalytic strong bond activation process, such as the aryl-halide bond. Traditionally, such a process of strong bond activation relied upon the use of transition metal complexes or strongly reducing photocatalysts in organic solvents. The generation of the aryl rad...

This review illustrates pioneering work and recent advancements on the use of pro-aromatic compounds as carbon- and heteroatom-radical precursors. Pro-aromatic systems such as 1,4-cyclohexadienes, dihydronicotinamides, 1,4-dihydropyridines, 4-substituted Hantzsch esters, pyridinium salts, and benzothiazolines are easily transformed to pro-aromatic...

Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama‐type hydration) is highly practical for alkene functionalization in complex synthesis. Different hydration protocols have been developed, however, control of the stereoselectivity remains a challenge. Herein, highly diastereoselective Fe‐catalyzed...

The highly diastereoselective Fe‐catalyzed anaerobic Markovnikov‐selective hydration of alkenes using nitroarenes as oxygenation reagents is reported. Abstract Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama‐type hydration) is highly practical for alkene functionalization in complex synthesis....

Hydrocyanation in the absence of toxic HCN gas is highly desirable. Addressing that challenge, transition-metal-catalyzed transfer hydrocyanation using safe HCN precursors has been developed, but these reagents generally require a Lewis acid for activation, and the control of regioselectivity often remains problematic. In this Letter, a Ni-catalyze...

Radical 1,3-trifluoromethylation/alkynylation of various allylboronic esters with concomitant 1,2-boron shift with alkynyl triflones is reported. These chain reactions proceed via CF3-radical addition to the allylic double bond, and the adduct radical undergoes 1,2-boron migration to give a translocated C-radical that is trapped by the alkynyl trif...

• Download : Download high-res image (124KB) • Download : Download full-size image Dr. Anup Bhunia is an Alexander von Humboldt postdoctoral fellow working at the Westfälische Wilhelms-Universität Münster in the lab of Prof. Armido Studer. He received his BSc in chemistry from Midnapore College, his MSc from the Indian Institute of Technology, and...

The catalytic transfer hydrocyanation represents a clean and safe alternative to hydrocyanation processes using the toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid catalyzed transfer hydrocyanation of...

Arynes are highly reactive intermediates, which are utilized for the electrophilic arylation of various X-H bonds (X = O, N, S etc.). Herein, a new synthetic strategy is demonstrated, where arynes are converted into aryl anion equivalents by treating with phosphines and a base. The addition of phosphines to arynes form the phosphonium salts, which...

The development of a cross-coupling method for the regi-oselective β-alkenylation of 2,5-cyclohexadiene carboxylic acid derivatives to form ortho-alkenylarenes through in situ decarboxylation and aromatization is described. The car-boxylic acid functionality is used as a traceless directing group for efficient and mild β-alkenylation. The modular s...

The N-heterocyclic carbene (NHC)-catalyzed enantioselective formal [3 + 2] annulation of α,β-unsaturated aldehydes with 3-hydroxy oxindoles is presented. Under oxidative conditions using the bisquinone oxidant, the reaction resulted in the synthesis of spiro γ-butyrolactones in moderate to good yields, enantioselectivity and diastereoselectivity. T...

In an attempt to develop the umpolung of Michael acceptors using chalcones having an enoate moiety under N-heterocyclic carbene (NHC) catalysis, a K3PO4-mediated intramolecular Rauhut–Currier type reaction was observed. This C(sp2)–C(sp2) coupling reaction afforded the biologically important 4H-chromenes in moderate to good yields. It is likely that...

Arynes are highly reactive intermediates having several applications in organic synthesis for the construction of various ortho-disubstituted arenes. Traditionally, arynes are generated in solution from haloarenes under strongly basic conditions. However, the scopes of many of the aryne reactions are limited because of the harsh conditions used for...

In an attempt to develop the umpolung of Michael acceptors using chalcones having an enoate moiety under N-heterocyclic carbene (NHC) catalysis, a K3PO4-mediated intramolecular Rauhut-Currier type reaction was observed. This C(sp(2))-C(sp(2)) coupling reaction afforded the biologically important 4H-chromenes in moderate to good yields. It is likely...

N-Heterocyclic carbene (NHC)-catalyzed formal [3 + 2] annulation of α,β-unsaturated aldehydes with N-substituted isatilidenes resulting in the diastereoselective synthesis of cyclopentanone-fused spirooxindoles is demonstrated. Mechanistically, the reaction proceeds via the generation of homoenolate equivalent intermediates from NHC and enals, whic...

The synthesis of deoxy-Breslow intermediates in the oxidized form has been developed by the reaction of N-heterocyclic carbenes (NHCs) with chalcones. Moreover, the initial tetrahedral adduct formed from the 1,4-addition of NHCs to chalcones is also isolated.

Transition-metal-free multicomponent reactions involving arynes, N-heterocycles, and various carbonyl compounds have been reported. With (iso)quinoline as the nucleophile and carbonyl compounds, such as aldehydes, ketones, and N-substituted isatins as electrophiles, the reaction afforded oxazino (iso)quinoline derivatives and the reaction proceeded...

An operationally simple multicomponent coupling involving in situ generated arynes from 2-(trimethylsilyl)aryl triflates, phosphines, and various acyclic and cyclic activated carbonyl compounds has been developed. The reaction proceeds via a formal [3 + 2] cycloaddition mode giving access to differently substituted (spiro)benzoxaphosphole derivativ...

The atom-economic and practical N-heterocyclic carbene (NHC) catalyzed Stetter reaction for the synthesis of γ-ketophosphonates by the reaction of aromatic aldehydes with vinylphosphonates is reported. The NHC derived from N-mesitylimidazolium salt (IMes) was an effective catalyst for this transformation, and the products were formed in moderate to...

Although nucleophilic phosphine-catalysis is a powerful tool for the construction of various carbocycles and heterocycles, the reactions in which phosphines are incorporated into the final product are rare, and the reports on phosphine addition to highly electrophilic arynes are scarce. Herein, we report the phosphine triggered multicomponent react...

N-Heterocyclic carbene (NHC)-catalyzed lactonization and lactamization of 2-bromoenals with heterocyclic C-H acids proceeding via the alpha,beta-unsaturated acyl azolium intermediates has been reported. The reaction furnished coumarin or quinolinone fused lactone/lactam derivatives. In addition, results of the enantioselective version of this react...

Mix and match: With isoquinoline as the nucleophilic trigger, multicomponent reactions afforded spirooxazino isoquinoline derivatives, proceeding through 1,4-dipolar intermediates. The use of pyridine as a nucleophile furnished indolin-2-one derivatives, with the reaction likely proceeding through a pyridylidene intermediate.

A mild, general, and transition-metal-free protocol for the synthesis of 9,10-dihydrophenanthrenes is reported. The aryne generated by the fluoride-induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates undergoes an efficient cascade reaction initiated by the Diels-Alder reaction with the differently substituted styrenes leading to the formati...

The multicomponent reaction involving arynes, quinolines, and aldehydes leading to the diastereoselective synthesis of benzoxazino quinoline derivatives in good yields proceeding via 1,4-zwitterionic intermediates is reported. In addition, the synthetic potential of various carbonyl compounds in this reaction as well as the utility of isoquinoline...

The N-heterocyclic carbene (NHC)-catalyzed generation of chiral a,b-unsaturated acylazoliums from 2-bromoenals followed by their interception with 1,3-dicarbonyl compounds or enamines, the formal [3+3] annulation reaction, is reported. The reaction results in the enantioselective synthesis of synthetically and medicinally important dihydropyran- an...

The N-heterocyclic carbene-catalyzed annulation of enals with 2'-hydroxy chalcones afford cyclopentane-fused coumarin derivatives with an excellent level of diastereocontrol. The reaction tolerates a broad range of functional groups; 25 examples are given, and a preliminary mechanistic investigation is provided.

A high-yielding, versatile and practical Diels-Alder reaction of pentafulvenes with arynes under mild reaction conditions is reported. The aryne generated by the fluoride induced 1,2-elimination of 2-(trimethylsilyl)aryl triflates undergoes efficient cycloaddition with 6-substituted and 6,6-disubstituted pentafulvenes leading to the formation of be...

The N-heterocyclic carbene-catalyzed intermolecular Stetter reaction of aldehydes with α,β-unsaturated sulfones allows the atom-economic and selective formation of γ-keto sulfones in good yields. Key to the success of this unique transition-metal-free carbon-carbon bond-forming reaction is the right choice of the NHC precursor and base. The reactio...

An efficient method for the synthesis of 2,3,5,6-tetrasubstituted tetrahydropyrans has been developed from the reaction of aldehydes and ethyl 2-(1-hydroxyalkyl/hydroxy(phenyl)methyl)-5-methylhex-4-enoate using (3,5)-oxonium-ene reaction promoted by boron trifluoride etherate in good yields under mild conditions.

This tutorial review is aimed at highlighting recent developments in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions utilizing a versatile class of reactive intermediates, viz., arynes, which hold the potential for numerous applications in organic synthesis. Key to the success of the resurgence of interest in the ri...