{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Ramirez M"],"funding":["Austrian Science Fund FWF","National Institute of General Medical Sciences","NIGMS NIH HHS","Natural Science Foundation of Jiangsu Province","National Science Foundation"],"pagination":["14989-14997"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8217342"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["60(27)"],"pubmed_abstract":["Strained cyclic allenes, first discovered in 1966 by Wittig and co-workers, have recently emerged as valuable synthetic building blocks. Previous experimental investigations, and computations reported here, demonstrate that the Diels-Alder reactions of furans and pyrroles with 1,2-cyclohexadiene and oxa- and azaheterocyclic analogs proceed with endo selectivity. This endo selectivity gives the adduct with the allylic saturated carbon of the cyclic allene endo to the diene carbons. The selectivity is very general and useful in synthetic applications. Our computational study establishes the origins of this endo selectivity. We analyze the helical frontier molecular orbitals of strained cyclic allenes and show how secondary orbital and electrostatic effects influence stereoselectivity. The LU"],"journal":["Angewandte Chemie (International ed. in English)"],"pubmed_title":["Origins of Endo Selectivity in Diels-Alder Reactions of Cyclic Allene Dienophiles."],"pmcid":["PMC8217342"],"funding_grant_id":["BK20190505","F31 GM130099","FWF, J 4216-N28","J 4216","J 4216-N28","R35 GM139593","F31 GM130099-02","R01 GM123299","R01 GM132432","CHE-1764328"],"pubmed_authors":["Garg NK","Houk KN","Svatunek D","Ramirez M","Liu F"],"additional_accession":[]},"is_claimable":false,"name":"Origins of Endo Selectivity in Diels-Alder Reactions of Cyclic Allene Dienophiles.","description":"Strained cyclic allenes, first discovered in 1966 by Wittig and co-workers, have recently emerged as valuable synthetic building blocks. Previous experimental investigations, and computations reported here, demonstrate that the Diels-Alder reactions of furans and pyrroles with 1,2-cyclohexadiene and oxa- and azaheterocyclic analogs proceed with endo selectivity. This endo selectivity gives the adduct with the allylic saturated carbon of the cyclic allene endo to the diene carbons. The selectivity is very general and useful in synthetic applications. Our computational study establishes the origins of this endo selectivity. We analyze the helical frontier molecular orbitals of strained cyclic allenes and show how secondary orbital and electrostatic effects influence stereoselectivity. The LU","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Jun","modification":"2025-04-29T11:30:15.23Z","creation":"2025-04-06T19:55:07.975Z"},"accession":"S-EPMC8217342","cross_references":{"pubmed":["33851504"],"doi":["10.1002/anie.202101809"]}}