Harnessing sulfur and nitrogen in the cobalt(III)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity - École polytechnique Accéder directement au contenu
Article Dans Une Revue Chemical Science Année : 2021

Harnessing sulfur and nitrogen in the cobalt(III)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity

Majji Shankar
Arijit Saha
Somratan Sau
Akhila Sahoo

Résumé

An unconventional cobalt(III)-catalyzed one-pot domino double annulation of aryl thioamides with unactivated alkynes is presented. Sulfur (S), nitrogen (N), and o,o′-C–H bonds of aryl thioamides are involved in this reaction, enabling access to rare 6,6-fused thiopyrano-isoquinoline derivatives. A reverse ‘S’ coordination over a more conventional ‘N’ coordination of thioamides to the Co-catalyst specifically regulates the formation of four [C–C and C–S at first and then C–N and C–C] bonds in a single operation, a concept which is uncovered for the first time. The power of the N-masked methyl phenyl sulfoximine (MPS) directing group in this annulation sequence is established. The transformation is successfully developed, building a novel chemical space of structural diversity (56 examples). In addition, the late-stage annulation of biologically relevant motifs and drug candidates is disclosed (17 examples). The preliminary photophysical properties of thiopyrano-isoquinoline derivatives are discussed. Density functional theory (DFT) studies authenticate the participation of a unique 6π-electrocyclization of a 7-membered S-chelated cobaltacycle in the annulation process
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hal-04477917 , version 1 (24-05-2024)

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Majji Shankar, Arijit Saha, Somratan Sau, Arghadip Ghosh, Vincent Gandon, et al.. Harnessing sulfur and nitrogen in the cobalt(III)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity. Chemical Science, 2021, 12 (18), pp.6393-6405. ⟨10.1039/D1SC00765C⟩. ⟨hal-04477917⟩
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