{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["21"],"submitter":["Tortora C"],"pubmed_abstract":["Asymmetric hydrocyanation of hydrazones, catalyzed by a calcium-BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations. Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a hydrocyanation via a calcium isocyanide complex, whereas the rate-limiting step is that which recovers the calcium catalyst and replaces the TMS-bound product from the catalys"],"journal":["Beilstein journal of organic chemistry"],"pagination":["755-765"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12018919"],"repository":["biostudies-literature"],"pubmed_title":["Development and mechanistic studies of calcium-BINOL phosphate-catalyzed hydrocyanation of hydrazones."],"pmcid":["PMC12018919"],"pubmed_authors":["Harder S","Tsogoeva SB","Kohlbauer S","Tortora C","Pahl J","Ballmann GM","Fischer CA","Zamfir A"],"additional_accession":[]},"is_claimable":false,"name":"Development and mechanistic studies of calcium-BINOL phosphate-catalyzed hydrocyanation of hydrazones.","description":"Asymmetric hydrocyanation of hydrazones, catalyzed by a calcium-BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations. Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a hydrocyanation via a calcium isocyanide complex, whereas the rate-limiting step is that which recovers the calcium catalyst and replaces the TMS-bound product from the catalys","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025","modification":"2025-07-01T03:05:48.323Z","creation":"2025-07-01T03:05:48.323Z"},"accession":"S-EPMC12018919","cross_references":{"pubmed":["40276279"],"doi":["10.3762/bjoc.21.59"]}}