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

Journal Article (Journal Article)

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, 14 N2 and 15 N2 isotopomers can be obtained, emphasizing a key trans-imination step when using 15 NH3 . In addition, we report the first experimental observation of 14 N/15 N isotopomers directly creating an asymmetric carbon. Finally, the 15 N2 -diazirine from l-tyrosine was hyperpolarized by a parahydrogen-based method (SABRE-SHEATH), demonstrating the products' utility as hyperpolarized molecular tag.

Full Text

Duke Authors

Cited Authors

  • Glachet, T; Marzag, H; Saraiva Rosa, N; Colell, JFP; Zhang, G; Warren, WS; Franck, X; Theis, T; Reboul, V

Published Date

  • August 2019

Published In

Volume / Issue

  • 141 / 34

Start / End Page

  • 13689 - 13696

PubMed ID

  • 31373802

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.9b07035

Language

  • eng