Synthesis, Table of Contents Synthesis DOI: 10.1055/a-2705-4564 Paper Published as part of the Special Issue in Honor of Dr. Dani Schultz, the 2025 Women in Chemistry Award Winner Structure–Reactivity Relationships of Anomeric Amide Reagents in Nitrogen Deletion Authors Author Affiliations Julia L. Driscoll 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Megan Morales 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Carys E. Obertone 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Bumsu Park 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Rubén Miguélez 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Mark D. Levin 1 Department of Chemistry, University of Chicago, Chicago, Illinois, United States Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract N-(benzyloxy)-N-(pivaloyloxy)benzamides, a class of anomeric amide reagents, have enabled nitrogen deletion of secondary amines as well as deamination and deaminative functionalization of primary amines in a single step. While the application of these reagents has been expanding, current use is limited by the substrate limitations of existing anomeric amides. This report details the design and synthesis of novel anomeric amide derivatives with improved reaction kinetics, one of which demonstrates improved deletion yields in some instances. These studies shed light on the stereoelectronic effects governing the reactivity of anomeric amides within the context of nitrogen-deletion reactions. Keywords KeywordsSkeletal editing - Stereo-electronic trends - Computational modeling - Atom deletion - Anomeric amide Full Text References References 1 Kennedy SH, Dherange BD, Berger KJ, Levin MD. Nature 2021; 593: 223 2 Wang Y, Bi C, Kawamata Y. et al. Nat Chem 2024; 16: 1539 3 Wang Y, Bogner M, Bailey J. et al. Nat Catal 2025; 08: 457 https://www.nature.com/articles/s41929-025-01336-3 4 Holovach S, Melnykov KP, Poroshyn I. et al. Chem Eur J 2023; 29: e202203470 5 Holovach SM, Melnykov KP, Poluektova MS, Rozhenko OB, Grygorenko OOJ. Org Pharm 2023; 21: 11 6 Wright BA, Matviitsuk A, Black MJ. et al. J Am Chem Soc 2023; 145: 10960 7 Tian D, Pan Y, Zhao X, Yin Y, Jiang Z. J Am Chem Soc. 2025 8 Gauthier M, Whittingham JBM, Hasija A, Tetlow DJ, Leigh DA. J Am Chem Soc 2024; 146: 29496 9 Deorkar N, Bahulekar R, Sorensen EJ, Achtenhagen M, Silldorff T. World Intellectual Property Organization WO2025053947A1 2025 10 Berger KJ, Driscoll JL, Yuan M, Dherange BD, Gutierrez O, Levin MD. J Am Chem Soc 2021; 143: 17366 11 Dherange BD, Yuan M, Kelly CB. et al. J Am Chem Soc 2023; 145: 17 12 Xue J-H, Li Y, Liu Y, Li Q, Wang H. Angew Chem Int Ed 2024; 63: e202319030 13 Kapoor M, Liu D, Young MC. J Am Chem Soc 2018; 140: 6818 14 Mansson CMF, Burns NZ. J Am Chem Soc 2022; 144: 19689 15 Shen L, Lin Z, Guo B, Zi W. Nat Synth 2022; 1: 883 16 Hui C, Brieger L, Strohmann C, Antonchick AP. J Am Chem Soc 2021; 143: 18864 17 Qin H, Cai W, Wang S, Guo T, Li G, Lu H. Angew Chem, Int Ed 2021; 60: 20678 18 Guo T, Li J, Cui Z, Wang Z, Lu H. Nat Synth 2024; 3: 913 19 Yokoi K, Renata H. Nat Commun 2025; 16: 1659 20 Glover SA, Hammond GP, Bonin AM. J Org Chem 1998; 63: 9684 21 Campbell JJ, Glover SA. J Chem Soc, Perkin Trans 2 1992; 1661 22 Campbell J, Glover A. J Chem Res 1999; 474 23 Cavanagh KL, Glover SA, Price HL, Schumacher RR. Aust J Chem 2009; 62: 700 24 Glover SA. Aust J Chem 2023; 76: 1 25 Berger KJ. C–N and C–H Bond Activation via New Reactive Intermediates and Hydrogen Atom Transfer Processes. The University of Chicago; 26 Blackmond DG. Angew Chem Int Ed 2005; 44: 4302 27 Thordarson P. Chem Soc Rev 2011; 40: 1305 28 Szostak R, Meng G, Szostak M. J Org Chem 2017; 82: 6373 29 Ielo L, Pace V, Holzer W. et al. Chem Eur J 2020; 26: 16246 30 Hutchby M, Houlden CE, Haddow MF, Tyler SNG, Lloyd-Jones GC, Booker-Milburn KI. Angew Chem Int Ed 2012; 51: 548 31 Brethomé AV, Fletcher SP, Paton RS. ACS Catal 2019; 9: 2313 32 Santiago CB, Milo A, Sigman MS. J Am Chem Soc 2016; 138: 13424 33 Williams WL, Zeng L, Gensch T, Sigman MS, Doyle AG, Anslyn EV. ACS Cent Sci 2021; 7: 1622 34 Haas BC, Kalyani D, Sigman MS. Sci Adv 2025; 11: eadt3013 35 Berger KJ, Dherange BD, Morales M, Driscoll JL, Tarhan AK, Levin MD. Org Synth 2023; 100: 113 Supplementary Material Supplementary Material Supplementary Material (PDF) (opens in new window)
