Copper(I)-Catalyzed Enantioselective 1,6-Borylation of α,β,γ,δ-Unsaturated Phosphonates

Abstract

Copper(I)-catalyzed asymmetric 1,6-borylation of 1,3-dienylphosphonates was achieved using (S,S)-Ph-BPE as a chiral ligand. Regio-, stereo-, and enantioselective borylation successfully proceeded to afford phosphonatecontaining allylboronates, with high enantioselectivity up to 97% ee. Further applications of the resulting products generated a valuable phosphonate analogue of γ-butyrolactone.Letter pubs.acs.org/OrgLett

Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

“…In 2018, Yun et al reported Cu-catalyzed enantioselective hydroboration of 1,1-disubstituted alkenes (Scheme 11b). 55 The reaction was found to be a new enantioselective method for the preparation of tertiary alkyl–Cu complexes that contain a C–Cu bond at the stereogenic center. In 2019, Hoveyda and Ito et al reported a Cu-catalyzed hydroboration of difluoro-substituted E -alkenes, affording the asymmetric synthesis of F-containing organic molecules (Scheme 11c).…”

Metal-free direct C–H phosphonation of N-heterocycles with diphenylphosphine oxides under mild conditions

“…were required in these reactions. [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Consequently, the development of concise and efficient strategies for C-P bond construction is a continuous research hotspot in organic chemistry. For instance, the Cui group reported a pioneering K 2 S 2 O 8 promoted C-H bond phosphonation of quinoxalin-2(1H)-ones with H-phosphinates or H-phosphine oxides.…”

Copper-Catalyzed Asymmetric Boroprotonation of Phosphinylallenes

“…Takacs and co-workers developed the rhodium-catalyzed asymmetric β- and γ-borylation of allylic phosphonates . Yun and co-workers also reported the copper-catalyzed enantioselective 1,6-borylation of 1,3-dienylphosphonates (Scheme a) . However, none of the above studies obtained chiral phosphorus compounds with α-carbon chirality.…”