Asymmetric synthesis of dibenzo[b, d]azepines by Cu-catalyzed reductive or borylative cyclization. Issue 46 (15th November 2021)

• Record Type: Journal Article
• Authors: Rodríguez-Salamanca, Patricia; Martín-de la Calle, Rocío; Rodríguez, Verónica; Merino, Pedro; Fernández, Rosario; Lassaletta, José M.; Hornillos, Valentín
• Is Part Of: Chemical science. Volume 12:Issue 46(2021)
• Page Start: 15291
• Page End: 15297
• Publication Date: 2021-11-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc04980a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Dibenzo[ b, d ]azepines featuring axially chiral 7-member-bridged biaryls have been prepared by asymmetric reductive or borylative cyclizations using copper catalysis. Abstract : A copper-catalyzed asymmetric intramolecular reductive cyclization for the synthesis of dibenzo[ b, d ]azepines is described. Use of 2′-vinyl-biaryl-2-imines as substrates and in situ formed [Cu I /(Ph-BPE)] as the catalyst enables the synthesis of 7-membered bridged biarylamines containing both central and axial stereogenic elements in high yields (up to 98%) and with excellent diastereo- and enantioselectivities (>20 : 1 d.r., up to 99% ee). Moreover, the same catalyst was found to facilitate a related borylative cyclization to afford versatile boronic ester derivatives. Both reactions proceed under mild conditions (rt) and are applicable to a variety of substituted aromatic and heterocyclic derivatives.