Preparation method for and application of chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand and iridium catalyst thereof

    公开(公告)号:US20230151035A1

    公开(公告)日:2023-05-18

    申请号:US17783648

    申请日:2020-12-17

    IPC分类号: C07F9/50 C07F15/00 B01J31/24

    摘要: The present invention relates to a preparation method for and an application of a chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand SpiroPNP and an iridium catalyst Ir-SpiroPNP thereof. The chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand is a compound represented by formula I, or a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and the main structural feature is a phosphine ligand having a chiral spiro indene skeleton and a large sterically hindered substituent. The chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand can be synthesized into a chiral starting material from a 7-diaryl/alkylphosphino-7′-amino-1,1′-spirodihydroindenyl compound having a spiro ring skeleton. The iridium catalyst of the chiral spirocyclic phosphino-7′-amino-1,1′-spirodihydroindenyl compound having a sprio ring skeleton. The iridium catalyst of the chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand is a compound represented by formula II, or a racemate or optical isomer thereof, or a catalytically acceptable salt thereof. The iridium catalyst can be used to catalyze the asymmetric catalytic hydrogenation of carbonyl compounds, and especially in the asymmetric catalytic hydrogenation of simple dialkyl ketones. Said catalyst exhibits high yield (>99%) and enantioselectivity (up to 99.8% ee), thus having practical value.

    Pincer-type ligand having acridane structure and metal complex using the same

    公开(公告)号:US11596934B2

    公开(公告)日:2023-03-07

    申请号:US17165636

    申请日:2021-02-02

    摘要: Disclosed are a pincer-type ligand having a structurally rigid acridane structure and a metal complex consisting of the pincer-type ligand and a metal bound to each other, and exhibiting high reactivity and stability during a variety of bonding activation reactions. T-shaped complexes can be prepared from acriPNP(4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide), which is a pincer-type PNP ligand having an acridane structure, and metal complexes, which can be structurally rigid and thus exhibit excellent reactivity and stability based on minimized structural change thereof, can be prepared by introducing an acridane structure into the backbone thereof. The PNP ligand is structurally stable and has novel chemical properties, as compared to conventional similar ligands, and thus can be utilized in a wide range of catalytic reactions and material chemistry.