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. 2020 Feb 12;142(6):3094-3103.
doi: 10.1021/jacs.9b12129. Epub 2020 Jan 22.

Synthesis of Cyclobutane-Fused Tetracyclic Scaffolds via Visible-Light Photocatalysis for Building Molecular Complexity

Martins S Oderinde  1 , Edna Mao  1 , Antonio Ramirez  2 , Joseph Pawluczyk  1 , Christine Jorge  3 , Lyndon A M Cornelius  1 , James Kempson  1 , Muthalagu Vetrichelvan  4 , Manivel Pitchai  4 , Anuradha Gupta  4 , Arun Kumar Gupta  4 , Nicholas A Meanwell  1 , Arvind Mathur  1 , T G Murali Dhar  1
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Synthesis of Cyclobutane-Fused Tetracyclic Scaffolds via Visible-Light Photocatalysis for Building Molecular Complexity

Martins S Oderinde et al. J Am Chem Soc. .

Abstract

We describe the synthesis through visible-light photocatalysis of novel functionalized tetracyclic scaffolds that incorporate a fused azabicyclo[3.2.0]heptan-2-one motif, which are structurally interesting cores with potential in natural product synthesis and drug discovery. The synthetic approach involves an intramolecular [2 + 2] cycloaddition with concomitant dearomatization of the heterocycle via an energy transfer process promoted by an iridium-based photosensitizer, to build a complex molecular architecture with at least three stereogenic centers from relatively simple, achiral precursors. These fused azabicyclo[3.2.0]heptan-2-one-based tetracycles were obtained in high yield (generally >99%) and with excellent diastereoselectivity (>99:1). The late-stage derivatization of a bromine-substituted, tetracyclic indoline derivative with alkyl groups, employing a mild Negishi C-C bond forming protocol as a means of increasing structural diversity, provides additional modularity that will enable the delivery of valuable building blocks for medicinal chemistry. Density functional theory calculations were used to compute the T1-S0 free energy gap of the olefin-tethered precursors and also to predict their reactivities based on triplet state energy transfer and transition state energy feasibility.

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