Stereoselective Palladium Catalyzed Allylic Phosphination

Abstract

Chiral enantiopure 2‐5‐diphenylphospholane borane 8 is an interesting nucleophile for allylic phosphination in the presence of palladium complexes to form CP bonds. A highly diastereoselective allylic phosphination reaction was realized using chiral palladium‐DACH‐naphthyl (DACH=1,2‐diaminocyclohexane) ligand as the catalyst system. The secondary phosphine‐borane complex could be classified as a NuL type nucleophile.

Photocurrent Generation through Charge‐Transfer Processes in Noncovalent Perylenediimide/DNA Complexes

“…As such, an efficient method for the synthesis of organophosphorus compounds with a chiral C–P center is highly desirable. Several strategies for C–P bond formation have emerged that employ P nucleophiles such as phosphines,2d,6 phenylphosphine borane,2e,7 phosphites,8 and phosphine oxides 9. In pioneering work, phosphine derivatives were examined in Pd‐catalyzed asymmetric allylations;2d only diphenylphosphine gave a good outcome and other phosphines offered unsatisfactory results 2d.…”

Palladacycle-Catalyzed Asymmetric Intermolecular Construction of Chiral Tertiary P-Heterocycles by Stepwise Addition of H–P–H Bonds to Bis(enones)

“…Recently, a few efficient strategies for the catalytic synthesis of chiral phosphines have emerged and attracted great interest. These include the synthesis of P-stereogenic phosphines via cross-coupling reactions and the synthesis of C-stereogenic phosphines via allylic phosphination as well as hydrophosphination of Michael acceptors such as conjugated esters, nitriles, enones, enals, and nitroalkenes . Nevertheless, the products obtained via the aforementioned methods are usually confined to chain phosphines (containing phosphorus atom(s) in the chain).…”

P–C Cross‐Coupling Onto Enamides: Versatile Synthesis of α‐Enamido Phosphane Derivatives

“…In light of the optimized conditions (Table 1, Entry 6), we envisaged performing the P–C cross‐coupling reaction of enol phosphates 2a – e with secondary phosphane derivatives 3a – d (Scheme , diphenylphosphane–borane 3a , chiral enantiopure phosphane–boranes 3b 11 and 3c ,12a and chiral phosphane oxide 3d ) 12b. The results are summarized in Table 2.…”