TY - JOUR

T1 - Taming diamines and acyl chlorides by carbon dioxide in selective mono-acylation reactions

AU - Lauridsen, Jerik Mathew Valera

AU - Poderyte, Margarita

AU - Lee, Ji Woong

N1 - Funding Information: The generous support of the Department of Chemistry, University of Copenhagen, from the Novo Nordisk Fonden (NNF20OC0064347) is gratefully acknowledged. The authors appreciate Yang Yang for preliminary experimental contributions and Maria Teresa Oliveira for proofreading. Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023

Y1 - 2023

N2 - Diamides are ubiquitous in chemical structures of organic molecules with a variety of applications. Most of these diamides are accessed via acylation of diamines with corresponding acyl donors, using a protecting group, or with excess amounts of diamines to prevent unwanted diacylation reactions. Here we report a practical and atom-economical method to access monoamide and unsymmetric diamides with diamines and stoichiometric amounts of acyl chlorides - the most accessible and highly reactive acyl donor. The reactivity of diamines can be controlled by CO2 as a green, temporary and traceless protecting group for monoacylation reactions, achieving high atom efficienty and low environmental factor. We demonstrated the utility of the method with a broad substrate scope and a large scale reaction, and performed control experiments to elucidate the origin of the high selectivity obtained with CO2. We showed that ambient CO2 from thin air affected the selectivity of monoacylation of diamines, implying the pervasive influence of atmospheric CO2 in organic synthesis.

AB - Diamides are ubiquitous in chemical structures of organic molecules with a variety of applications. Most of these diamides are accessed via acylation of diamines with corresponding acyl donors, using a protecting group, or with excess amounts of diamines to prevent unwanted diacylation reactions. Here we report a practical and atom-economical method to access monoamide and unsymmetric diamides with diamines and stoichiometric amounts of acyl chlorides - the most accessible and highly reactive acyl donor. The reactivity of diamines can be controlled by CO2 as a green, temporary and traceless protecting group for monoacylation reactions, achieving high atom efficienty and low environmental factor. We demonstrated the utility of the method with a broad substrate scope and a large scale reaction, and performed control experiments to elucidate the origin of the high selectivity obtained with CO2. We showed that ambient CO2 from thin air affected the selectivity of monoacylation of diamines, implying the pervasive influence of atmospheric CO2 in organic synthesis.

U2 - 10.1039/d2gc04478a

DO - 10.1039/d2gc04478a

M3 - Letter

AN - SCOPUS:85147755455

VL - 25

SP - 1332

EP - 1338

JO - Green Chemistry

JF - Green Chemistry

SN - 1463-9262

IS - 4

ER -