{"database":"biostudies-literature","file_versions":[],"scores":{"citationCount":0,"reanalysisCount":0,"viewCount":56,"searchCount":0},"additional":{"submitter":["Dabrowski JA"],"funding":["NIGMS NIH HHS"],"pagination":["4778-81"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC3069135"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["133(13)"],"pubmed_abstract":["A catalytic enantioselective method for the formation of alkyne-substituted all-carbon quaternary stereogenic centers is reported. Additions of alkynylaluminums to alkyl-, aryl-, carboxylic ester-, or silyl-substituted allylic phosphates are promoted by 1.0-5.0 mol % loadings of NHC-Cu complexes derived from air-stable and commercially available CuCl(2)·2H(2)O. The requisite Al-based reagents are prepared through treatment of the corresponding aryl-, heteroaryl-, alkyl-, or alkenyl-substituted terminal alkynes with diisobutylaluminum hydride in the presence of 5.0 mol % Et(3)N at ambient temperature. The desired 1,4-enynes are obtained in up to 98% yield and >99:1 enantiomeric ratio. Selected Au-catalyzed cyclizations involving the alkyne unit of the enantiomerically enriched products are presented as a demonstration of the method's utility in chemical synthesis."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Enantioselective synthesis of alkyne-substituted quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution reactions with (i-Bu)2(alkynyl)aluminum reagents."],"pmcid":["PMC3069135"],"funding_grant_id":["GM-47480","R01 GM057212","R37 GM047480-20","R37 GM047480","R01 GM047480"],"pubmed_authors":["Hoveyda AH","Dabrowski JA","Gao F"],"view_count":["56"],"additional_accession":[]},"is_claimable":false,"name":"Enantioselective synthesis of alkyne-substituted quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution reactions with (i-Bu)2(alkynyl)aluminum reagents.","description":"A catalytic enantioselective method for the formation of alkyne-substituted all-carbon quaternary stereogenic centers is reported. Additions of alkynylaluminums to alkyl-, aryl-, carboxylic ester-, or silyl-substituted allylic phosphates are promoted by 1.0-5.0 mol % loadings of NHC-Cu complexes derived from air-stable and commercially available CuCl(2)·2H(2)O. The requisite Al-based reagents are prepared through treatment of the corresponding aryl-, heteroaryl-, alkyl-, or alkenyl-substituted terminal alkynes with diisobutylaluminum hydride in the presence of 5.0 mol % Et(3)N at ambient temperature. The desired 1,4-enynes are obtained in up to 98% yield and >99:1 enantiomeric ratio. Selected Au-catalyzed cyclizations involving the alkyne unit of the enantiomerically enriched products are presented as a demonstration of the method's utility in chemical synthesis.","dates":{"release":"2011-01-01T00:00:00Z","publication":"2011 Apr","modification":"2020-10-29T12:12:13Z","creation":"2019-03-26T23:28:43Z"},"accession":"S-EPMC3069135","cross_references":{"pubmed":["21384918"],"doi":["10.1021/ja2010829"]}}