{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Hao H"],"funding":["National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["4411-4414"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9107076"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["23(11)"],"pubmed_abstract":["Lone pair-π (LP-π) interactions between Lewis basic heteroatoms, such as oxygen and sulfur, and electron-deficient π systems are important noncovalent interactions. However, they have seldom been used to control catalyst-substrate interactions in catalysis. We performed density functional theory calculations to investigate the strengths of LP-π interactions between different lone pair donors and cationic π systems, and in different complexation geometries. Energy decomposition analysis calculations indicated that the dominant stabilizing force in LP-π complexes is electrostatic interaction and the electrostatic potential surface of the π system predicts the most favorable site for forming LP-π complexes. Benzotetramisole (BTM) is revealed as a privileged acyl transfer catalyst that promotes LP-π interactions because the positive charge of the acylated BTM is delocalized onto the dihydroimidazole ring, which binds strongly with a variety of oxygen and sulfur lone pair donors."],"journal":["Organic letters"],"pubmed_title":["Energy Decomposition Analysis Reveals the Nature of Lone Pair-π Interactions with Cationic π Systems in Catalytic Acyl Transfer Reactions."],"pmcid":["PMC9107076"],"funding_grant_id":["R35 GM128779","U01 GM125290","R35GM128779","U01GM125290"],"pubmed_authors":["Qi X","Liu P","Hao H","Tang W"],"additional_accession":[]},"is_claimable":false,"name":"Energy Decomposition Analysis Reveals the Nature of Lone Pair-π Interactions with Cationic π Systems in Catalytic Acyl Transfer Reactions.","description":"Lone pair-π (LP-π) interactions between Lewis basic heteroatoms, such as oxygen and sulfur, and electron-deficient π systems are important noncovalent interactions. However, they have seldom been used to control catalyst-substrate interactions in catalysis. We performed density functional theory calculations to investigate the strengths of LP-π interactions between different lone pair donors and cationic π systems, and in different complexation geometries. Energy decomposition analysis calculations indicated that the dominant stabilizing force in LP-π complexes is electrostatic interaction and the electrostatic potential surface of the π system predicts the most favorable site for forming LP-π complexes. Benzotetramisole (BTM) is revealed as a privileged acyl transfer catalyst that promotes LP-π interactions because the positive charge of the acylated BTM is delocalized onto the dihydroimidazole ring, which binds strongly with a variety of oxygen and sulfur lone pair donors.","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Jun","modification":"2025-04-22T13:07:35.113Z","creation":"2025-04-06T00:29:05.091Z"},"accession":"S-EPMC9107076","cross_references":{"pubmed":["34010010"],"doi":["10.1021/acs.orglett.1c01351"]}}