Iodonitrene in Action: Direct Transformation of Amino Acids into Terminal Diazirines and 15 N2 -Diazirines and Their Application as Hyperpolarized Markers

Journal of the American Chemical Society
Thomas GlachetVincent Reboul

Abstract

A one-pot metal-free conversion of unprotected amino acids to terminal diazirines has been developed using phenyliodonium diacetate (PIDA) and ammonia. This PIDA-mediated transformation occurs via three consecutive reactions and involves an iodonitrene intermediate. This method is tolerant to most functional groups found on the lateral chain of amino acids, it is operationally simple, and it can be scaled up to provide multigram quantities of diazirine. Interestingly, we also demonstrated that this transformation could be applied to dipeptides without racemization. Furthermore, 14N2 and 15N2 isotopomers can be obtained, emphasizing a key trans-imination step when using 15NH3. In addition, we report the first experimental observation of 14N/15N isotopomers directly creating an asymmetric carbon. Finally, the 15N2-diazirine from l-tyrosine was hyperpolarized by a parahydrogen-based method (SABRE-SHEATH), demonstrating the products' utility as hyperpolarized molecular tag.

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Citations

Jun 7, 2019·Angewandte Chemie·Guannan ZhangWarren S Warren
May 18, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Muhammad Murtaza Hassan, Olasunkanmi O Olaoye
Sep 2, 2020·Scientific Reports·Hye Jin JeongKeunhong Jeong
Oct 18, 2020·Applied Microbiology and Biotechnology·Xu TanJing Wu
Jun 15, 2021·Magnetic Resonance in Chemistry : MRC·Keilian MacCullochThomas Theis
Jun 26, 2021·Chemical Science·Louis P ConwayChristopher G Parker
Nov 9, 2021·Journal of the American Chemical Society·Chunngai HuiAndrey P Antonchick

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