Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones via dynamic kinetic resolution

Abstract

A new class of tunable heterophosphole dimeric ligands have been designed and synthesized.

Recent Progress and Applications of Transition-Metal-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of Ketones and Imines through Dynamic Kinetic Resolution

“…Kozlowski and co-workers designed, in 2018, a new series of highly modular and tunable heterophosphole dimeric ligands that proved to be effective chiral inducers in the first copper-catalyzed AH of racemic 2-substituted 1tetralones and related heteroaryl ketones through DKR that furnished the corresponding optically enriched 2-substituted 1-tetralols (Scheme 4). 11 Optimization of the reaction parameters revealed that the catalytic system composed of CuCl 2 , electron-rich P(3,5-xylyl) 3 as ancillary phosphine, and the electron-poor azaphosphole N-BABIPhos L3 was…”

Manganese‐Catalyzed anti‐Selective Asymmetric Hydrogenation of α‐Substituted β‐Ketoamides

“…To our knowledge, only one copper catalyst system and one nickel catalyst system have been reported to date, respectively, for dynamic kinetic asymmetric hydrogenation of racemic α‐substituted ketones (Scheme B), although the catalyst loadings remained relatively high. Recently, we developed a series of structurally well‐defined Mn I complexes ( 1 ) containing lutidine‐based chiral pincer ligands for highly efficient enantioselective hydrogenation of various simple ketones .…”

Modular Dihydrobenzoazaphosphole Ligands for Suzuki–Miyaura Cross-Coupling

“…Purification by column chromatography on silica gel (CH 2 Cl 2 /MeOH, 96:4) gave 7b as a yellow solid; yield: 4.53 g (64%); mp 195-197 °C. 1 H NMR (400 MHz, CDCl 3 ): δ = 7.61 (d,J = 8.5 Hz,2 H),3 H),7.31 (t,J = 8.4 Hz, 1 H), 7.15 (dd, J = 8.3, 3.50 Hz, 1 H), 6.79 (dd, J = 7.4, 3.5 Hz, 1 H), 6.67 (d, J = 8.3 Hz, 2 H), 6.57 (d,J = 8.3 Hz,2 H) 9,126.6,125.5,124.7 (d,J = 40.6 Hz),120.6,117.3,104.4,103.0,55.7 (d,J = 76.5 Hz)…”

“…The new dihydrobenzoazaphosphole ligands employed in this study were prepared starting from the key phenol building block rac-3 that was obtained in 5 steps from arene 2 according to our previously reported procedures (Scheme 2). 9 After conversion of 3 to triflate 4, Negishi cross-coupling 10 with dimethoxyphenylzinc bromide (DMPZnBr) provided access to the biaryl phosphine oxide 5. After the pivalate group was removed under basic conditions, Buchwald-Hartwig 11 amination with amine 6 and various aryl bromides afforded phosphine oxides 7.…”