Bulky P*‐Chirogenic Diazaphospholidines as Monodentate Ligands for Asymmetric Catalysis

Abstract

A series of easily prepared bulky P*-chiral diamidophosphites based on (2R,5S)-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane and (2R,5S)-3-(p-bromophenyl)-1,3-diaza-2-phosphabicyclo[3.3.0]octane backbones have been designed and developed. Ligands of this type exhibited high enantioselectivities in Pd-catalysed allylic substitution reactions of (E)-1,3-diphenylallyl acetate with NaSO 2 pTol (up to 87 % ee), CH 2 (CO 2 Me) 2 (up to 92 % ee), (C 3 H 7 ) 2 NH (up to 93 % ee) and (CH 2 ) 4 NH (up to 99 % ee). These novel stereoselectors

Pd(II) complexes of monodentate deoxycholic acid derived binaphthyl diamido phosphites as chiral catalysts in the asymmetric Suzuki-Miyaura cross-coupling

“…Chiral diamidophosphites, both mono-and bidentate, have been used in different enantioselective C-C bond forming reactions, such as Pd-catalyzed allylic substitutions, 8 Pd-catalyzed cycloaddition, 9 Pd-catalyzed hydrovinylation, 10 Rh-catalyzed hydroformylation, 11 Cu and Rh-catalyzed conjugate addition of organometallic reagents to enones. 12 However, despite the success obtained in different Pd-catalyzed enantioselective reactions, to the best of our knowledge no examples concerning the use of diamidophosphite ligands in the Pdcatalyzed asymmetric Suzuki-Miyaura cross-coupling reaction are reported in the literature, although this reaction has received a great deal of attention because of the interest in the biaryl reaction products, whose structural motif is present in chiral auxiliaries 1c as well as in bioactive compounds. 13 Other kind of chiral phosphorus ligands have been used to this aim, mainly bidentate ligands, such as bishydrazones 14 or phosphine-carbene ligands, 15 and bulky monophosphines.…”

“…3 J HH =1.2 Hz, e'), 4.72 (m, 1H, 3), 4.28 (dt, 3 J HP =7.8 Hz, 3 J HH =2.6 Hz, 1H, 12), 3.40 (s, 3H, OCH 3 ), 2.92 (d, 3 J HP =9.1 Hz, 3H, NMe), 2.89 (d, 3 J HP =13.2 Hz, 3H, NMe'), 2.24 (m, 1H, 23), 2.14 (m, 1H, 23), 1.96-1.78 (m, 6H, 1, 1 H NMR (400 MHz, 298 K, C 6 D 6 ), δ: 7.95 (d, 3 J HH =8.6 Hz, b), 7.80-7.68 (m, 4H, a', b', c, c'), 7.66 (d, 3 J HH =8.6 Hz, a), 7.43 (d, 3 J HH =8.7 Hz, 1H, f), 7.40 (d, 3 J HH =8.5 Hz, f'), 7. 2H, d, d'), 2H, e, e'), 4.91 (m, 1H,3), 4.35 (br s, 1H,12), 3.40 (s, 3H, OCH 3 ), 3.03 (d,3 J HP =7.6…”