A Combination of Computational and Experimental Studies to Correlate Electronic Structure and Reactivity of Donor–Acceptor Singlet Carbenes

Shweta Singh; Ludovic Gremaud; Subhabrata Sen; Debajit Maiti

doi:10.1055/a-2153-6819

Synlett, Table of Contents

Synlett 2024; 35(03): 319-324
DOI: 10.1055/a-2153-6819

cluster

Organic Chemistry Under Visible Light: Photolytic and Photocatalytic Organic Transformations

A Combination of Computational and Experimental Studies to Correlate Electronic Structure and Reactivity of Donor–Acceptor Singlet Carbenes

Authors

Shweta Singh

^aDept. of Chemistry, School of Natural Sciences, Shiv Nadar Institution of Eminence Deemed to be University, Tehsil Dadri, Gautam Buddha Nagar, U.P. 201314, India
Ludovic Gremaud

^bUniversity of Applied Sciences Western Switzerland, Faculty of Engineering and Architecture, Department of Chemistry, Pérolles 80, Fribourg 1700, Switzerland
Subhabrata Sen∗

^aDept. of Chemistry, School of Natural Sciences, Shiv Nadar Institution of Eminence Deemed to be University, Tehsil Dadri, Gautam Buddha Nagar, U.P. 201314, India
Debajit Maiti∗

^aDept. of Chemistry, School of Natural Sciences, Shiv Nadar Institution of Eminence Deemed to be University, Tehsil Dadri, Gautam Buddha Nagar, U.P. 201314, India

Abstract

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Abstract

Most of the reactivities of donor–acceptor (D–A) singlet carbenes are similar to metal carbenoids. However, the lone pair at the carbenoid carbon, coordinated with metal, is free in D–A carbene thereby making it nucleophilic as well. Herein, DFT-optimized structural features of D–A carbene has been investigated and is compared with rhodium carbenoid. It was observed that, when a D–A carbene reacts with cyclic-1,3-diones in different ethereal solvents, it is the lone pair at the sp² orbital of the carbene that abstracts the proton from the enol form (of the cyclic-1,3-diones) to form a benzylic carbocation and an enolate. Subsequently, the carbocation undergoes nucleophilic attack by O of the ether solvents and then by the enolate to afford the desired ether-linked products. Accordingly, herein the reaction in THF, which otherwise had failed to work as a substrate in reported amino etherification reactions, worked well. DFT-calculated orbital energy levels and reaction profile support this reverse reactivity of singlet carbenes. Furthermore, HOMO–LUMO calculations indicated that electron-rich arenes in D–A carbene stabilizes the LUMO and destabilizes the HOMO which increases yield. Additionally, a library of 37 enol ether and 39 ether-linked compounds of potential medicinal relevance have been synthesized with good to excellent yields using numerous cyclic-1,3-diones.

Key words

carbene chemistry - singlet carbene - DFT calculation - photochemical reaction

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References

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