Research Project: Synthesis Of Deuterated active pharmaceutical ingredients via early and late stage c-h functionalizaiton in the presence of recyclable heterogeneous visible light photocatalysts
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Contributors
Funders
ID
TB.00695
Authors
Palani, Natarajan
Researcher
Publications
Facile preparation of N-tert-butyl amides under heat-, metal- and acid-free conditions by using tert-butyl nitrite (TBN) as a practical carbon source
(Royal Society of Chemistry, 2023) Palani, Natarajan; Metin, Önder; KUYTAM (Koç University Surface Science and Technology Center); Department of Chemistry; Yes; College of Sciences; Research Center
Tert-Butyl nitrite (TBN) is a nontoxic substance that has frequently been used as a source of nitrogen, oxygen, or nitric oxide (NO), but not as a carbon source in chemical transformations. Here, for the first time to the best of our knowledge, we introduced TBN as a source of carbon (tert-butyl group) for the synthesis of highly valuable N-tert-butyl amides from nitriles and water under very mild conditions.
Activation of DMSO(-d6) via heterogeneous photo-Fenton-like process with in situ production of Hydroxyl radicals for the C-H (trideutero)methylation of (iso)quinoliniums
(Royal Soc Chemistry, 2023) Palani, Natarajan; Metin, Önder; Başak, Aleyna; KUYTAM (Koç University Surface Science and Technology Center); Department of Chemistry; Graduate School of Sciences and Engineering; Yes; College of Sciences; GRADUATE SCHOOL OF SCIENCES AND ENGINEERING; Research Center
To activate dimethyl sulfoxide (DMSO, CH3SOCH3) as a methylation agent in the C-H functionalization of (iso)quinoliniums (1), a heterogeneous photo-Fenton-like method involving the in situ generation of hydroxyl radicals by a gCN/MnO/MnO(OH) photocatalyst under visible light irradiation was realized for the first time. In the developed methodology, only a small amount of gCN/MnO/MnO(OH) photocatalysts (15 mg) was needed for the methylation of (iso)quinoliniums (1.0 mmol-scale of 1) to achieve moderate to good yields of the expected methylated-products (2) under ambient conditions. Mechanistically, hydroxyl radicals (OH) are produced when the gCN/MnO/MnO(OH) photocatalyst reacts with H2O and O-2 under visible light illumination, and then they are added to DMSO, where they subsequently fragment into CH3 radicals. The product is generated via the nucleophilic attack of the CH3 radical at the most electron-deficient position of 1, followed by deprotonation reaction. The same procedure could also be used to create trideuteromethylated (iso)quinolines (3) when DMSO-d(6) (CD3SOCD3) was used in place of DMSO. The presented novel strategy for DMSO or DMSO-d(6) activation herein is more practical, cost-effective, and risk-free compared to the conventional Fenton reagent (H2O2 and Fe2+/Fe3+) systems available in the literature. Additionally, the gCN/MnO/MnO(OH) photocatalyst is easy to prepare, practical and economical together with being easy recoverable and reusable for several runs without considerable loss in its initial activity.
