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Site-selective aromatic C-H λ³-iodanation with a cyclic iodine(iii) electrophile in solution and solid phases.

ABSTRACT: An efficient and site-selective aromatic C-H λ³-iodanation reaction is achieved using benziodoxole triflate (BXT) as an electrophile under room temperature conditions. The reaction tolerates a variety of electron-rich arenes and heteroarenes to afford the corresponding arylbenziodoxoles in moderate to good yields. The reaction can also be performed mechanochemically by grinding a mixture of solid arenes and BXT under solvent-free conditions. The arylbenziodoxoles can be used for various C-C and C-heteroatom bond formations, and are also amenable to further modification by electrophilic halogenation. DFT calculations suggested that the present reaction proceeds via a concerted λ³-iodanation-deprotonation transition state, where the triflate anion acts as an internal base.

SUBMITTER: Ding W

PROVIDER: S-EPMC8159425 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Polyphosphates (polyPs) are ubiquitous polymers in living organisms from bacteria to mammals. They serve a wide variety of biological functions, ranging from energy storage to stress response. In the last two decades, polyPs have been primarily viewed as linear polymers with varying chain lengths. However, recent biochemical data show that small metaphosphates, cyclic oligomers of [PO3](-), can bind to the enzymes ribonuclease A and NAD kinase, raising the question of whether metaphosphates can occur naturally as products of biological activity. Before the 1980s, metaphosphates had been reported in polyPs extracted from various organisms, but these results are considered artifactual due to the extraction and purification protocols. Here, we employ nondestructive 31P solid-state NMR spectroscopy to investigate the chemical structure of polyphosphates in whole cells as well as insoluble fractions of the bacterium Xanthobacter autotrophicus. Isotropic and anisotropic 31P chemical shifts of hydrated whole cells indicate the coexistence of linear and cyclic phosphates. Under our cell growth conditions and the concentrated conditions of the solid-state NMR samples, we found substantial amounts of cyclic phosphates in X. autotrophicus, suggesting that in fresh cells metaphosphate concentrations can be significant. The cellular metaphosphates are identified by comparison with the 31P chemical shift anisotropy of synthetic metaphosphates of known structures. In X. autotrophicus, the metaphosphates have a chemical shift anisotropy that is consistent with an average size of 3-8 phosphate units. These metaphosphates are enriched in insoluble and electron-dense granules. Exogenous hexametaphosphate added to X. autotrophicus cell extracts is metabolized to trimetaphosphates, supporting the presence and biological role of metaphosphates in cells. The definitive evidence for the presence of metaphosphates, reported here in whole bacterial cells for the first time, opens the path for future investigations of the biological function of metaphosphates in many organisms.

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Site-selective aromatic C-H λ³-iodanation with a cyclic iodine(iii) electrophile in solution and solid phases.

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Site-selective aromatic C-H λ3-iodanation with a cyclic iodine(iii) electrophile in solution and solid phases.

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OmicsDI is part of the ELIXIR infrastructure

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Site-selective aromatic C-H λ³-iodanation with a cyclic iodine(iii) electrophile in solution and solid phases.