Plus‐Size DiPAMP Hybrids for Advanced Rhodium(I)‐Catalyzed Hydrogenation: The 2RBigFUS Model

Abstract

Outfitting the P,P'‐distereogenic 2MeBigFUS ligand with the characteristic branched/functionalized‐alkoxy feature of the R‐SMS‐Phos design furnished the 2RBigFUS family (Figure 2). Rhodium(I) complexes thereof exhibited a further boosted activity and superior enantioselectivity in the hydrogenation of various functionalized olefins, including the synthetically challenging a‐arylacrylic acids. The application under practical conditions to enantiomeric active pharmaceutical ingredients (APIs) and relevant synthetic building blocks capped the outcome.

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

“…It should be noted that very high enantioselectivities (>98% ee) have been observed in many cases, especially when employing electronrich and conformationally rigid ligands. Furthermore, significantly high turnover numbers (TONs) (>10 000) have been achieved in the hydrogenations with TangPhos, 40 DiSquar-eP*, 171 SMS-Phos, 184 BenzP*, 189 TMB-QuinoxP*, 196 2i-PrBigFUS, 219 POP, 235 and L79. 236 These results suggest that analogous electron-rich ligands such as TCFP, 41 DuanPhos, 42 ZhangPhos, 186 and BulkyP* 252 may exhibit similarly high TONs.…”

“…The C 2 -symmetric P-stereogenic bisphosphorus ligands reported from 2001 to 2023 are shown in Figure , in the order of their publication years. ,− ,,,− A tetraphosphine ligand L41 and a C 3 -symmetric triphosphine ligand MT-Siliphos are also included in this figure as exceptions. All of these ligands possess unique structural and electronic properties, arising from the two different substituents on the phosphorus atoms and the ligand backbones, and exhibit their characteristic reactivities and stereoselectivities in various transition-metal-catalyzed asymmetric reactions.…”

[Metal–Diphosphine]-Catalyzed Asymmetric Hydrogenation of β-Amido β-Substituted Acrylates: A Practical Literature Overview

“…Also, cat AS ium T performed well, albeit under 8 bar H 2 , giving 99% ee for the E isomer and 93% for the Z isomer. Finally, applying the relevant cutoff threshold of 95% ee for MAB and ( Z )- MAPA results in a few systems standing out. For this, see Tables and and ref . …”

“…Finally, applying the relevant cutoff threshold of 95% ee for MAB and ( Z )- MAPA results in a few systems standing out. For this, see Tables and and ref .…”

“… a Refer to the Table footnotes for details. b Some ligands were excluded due to unclear conditions (see Table ). c See ref for the acid. …”