Synthesis of Chiral Hypervalent Trifluoromethyl Organobismuth Complexes and Enantioselective Olefin Difluorocarbenation Screenings.

Autor: Louis-Goff T; Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, Hawaii, 96822, USA., Trinh HV; Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, Hawaii, 96822, USA.; Present Address: Chemical Engineering in Advanced Materials and Renewable Energy Research Group, School of Engineering and Technology, Van Lang University, Ho Chi Minh City, Vietnam., Chen E; Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, Hawaii, 96822, USA.; Present Address: John A. Burns School of Medicine, 651 Ilalo St, Honolulu, HI, 96813, USA., Rheingold AL; Department of Chemistry, University of California, San Diego La Jolla, California, 92093, USA., Hyvl J; Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, Hawaii, 96822, USA.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2023 Feb; Vol. 88 (2), pp. e202200450.
DOI: 10.1002/cplu.202200450
Abstrakt: Two hypervalent trifluoromethyl organobismuth complexes were prepared from commercially available chiral amines, (R)-1-cyclohexylethylamine and (1R, 2R, 3R, 5S)-(-)-isopinocampheylamine; however, only the complex from the latter amine was prepared as a single stereoisomer. Both organobismuth complexes were fully characterized by NMR spectroscopy and single-crystal X-ray crystallography, revealing that the structures were similar to previously reported complexes with a hypervalent Bi-N bond. The complexes were catalytically active in olefin difluorocarbenation with Ruppert-Prakash reagent (TMS-CF 3 ) used as a terminal source of CF 2 . The catalyst derived from isopinocampheylamine was screened with three prochiral olefins of various reactivity in DCM and toluene. All reactions afforded the 1,1-difluorocyclopropanes in good yields, but no enantiomeric excess was observed.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje