642-28-4Relevant academic research and scientific papers
Bio-inspired asymmetric aldehyde arylations catalyzed by rhodium-cyclodextrin self-inclusion complexes
Asahi, Kaoru,Fujiwara, Shin-Ichi,Iwasaki, Takanori,Kambe, Nobuaki,Takahashi, Ryota,Tsuda, Susumu,Ueda, Ryoji,Yamauchi, Hiroki
supporting information, p. 801 - 807 (2022/02/03)
Transition-metal catalysts are powerful tools for carbon-carbon bond-forming reactions that are difficult to achieve using native enzymes. Enzymes that exhibit inherent selectivities and reactivities through host-guest interactions have inspired widesprea
Binaphthyl-prolinol chiral ligands: Design and their application in enantioselective arylation of aromatic aldehydes
Yao, Chao,Chen, Yaoqi,Sun, Ruize,Wang, Chao,Huang, Yue,Li, Lin,Li, Yue-Ming
supporting information, p. 3644 - 3655 (2021/05/04)
Binaphthyl-prolinol ligands were designed and applied in enantioselective arylation of aromatic aldehydes and sequential arylation-lactonization of methyl 2-formylbenzoate. Under optimized conditions, the reactions provided the desired diarylmethanols and 3-aryl phthalides in up to 96% yields with up to 99% ee and up to 89% yields with up to 99% ee, respectively. In particular, essentially optically pure 3-aryl phthalides (over 99% ee) were obtained in large quantities through recrystallization. This journal is
Pd-catalyzed allylative dearomatisation using Grignard reagents
Boldrini, Cosimo,Harutyunyan, Syuzanna R.
supporting information, p. 11807 - 11810 (2021/11/30)
Pd-catalyzed allylative dearomatisation of naphthyl halides is shown to be feasible by employing Grignard reagents. The high reactivity of the nucleophile allows for fast reactions and low catalyst loading, while a plethora of successfully substituted compounds illustrate the broad scope. Five membered heteroaromatic compounds are also demonstrated to be reactive under similar conditions.
Synthesis of Triarylmethanes via Palladium-Catalyzed Suzuki-Miyaura Reactions of Diarylmethyl Esters
Dardir, Amira H.,Casademont-Reig, Irene,Balcells, David,Ellefsen, Jonathan D.,Espinosa, Matthew R.,Hazari, Nilay,Smith, Nicholas E.
supporting information, p. 2332 - 2344 (2021/06/28)
The synthesis of triarylmethanes via Pd-catalyzed Suzuki-Miyaura reactions between diarylmethyl 2,3,4,5,6-pentafluorobenzoates and aryl boronic acids is described. The system operates under mild conditions and has a broad substrate scope, including the coupling of diphenylmethanol derivatives that do not contain extended aromatic substituents. This is significant as these substrates, which result in the types of triarylmethane products that are prevalent in pharmaceuticals, have not previously been compatible with systems for diarylmethyl ester coupling. Furthermore, the reaction can be performed stereospecifically to generate stereoinverted products. On the basis of DFT calculations, it is proposed that the oxidative addition of the diarylmethyl 2,3,4,5,6-pentafluorobenzoate substrate occurs via an SN2 pathway, which results in the inverted products. Mechanistic studies indicate that oxidative addition of the diarylmethyl 2,3,4,5,6-pentafluorobenzoate substrates to (IPr)Pd(0) results in the selective cleavage of the O-C(benzyl) bond in part because of a stabilizing η3-interaction between the benzyl ligand and Pd. This is in contrast to previously described Pd-catalyzed Suzuki-Miyaura reactions involving phenyl esters, which involve selective cleavage of the C(acyl)-O bond, because there is no stabilizing η3-interaction. It is anticipated that this fundamental knowledge will aid the development of new catalytic systems, which use esters as electrophiles in cross-coupling reactions.
P-chirogenic Trost ligands mediated asymmetric hydrogenation of simple ketones
Du, Peng,Liu, Yan-Lan,Lu, Xiao-Bing
supporting information, (2020/09/22)
Herein, we report a highly active catalyst system consisting of (Rc,Rc,Rp,Rp)-P-chirogenic Trost ligand and [Ru(C6H6)Cl2]2 for asymmetric hydrogenation of simple ketones, affording the corresponding optically active alcohols in moderate enantioselectivity. A synergetic effect between P- and C-chirogenic centers of the P-chirogenic Trost ligands was observed in this asymmetric hydrogenation process.
Bulky N-Heterocyclic-Carbene-Coordinated Palladium Catalysts for 1,2-Addition of Arylboron Compounds to Carbonyl Compounds
Okuda, Yuta,Nagaoka, Masahiro,Yamamoto, Tetsuya
, p. 6291 - 6300 (2020/11/30)
The synthesis of primary, secondary, and tertiary alcohols by the 1,2-addition of arylboronic acids or boronates to carbonyl compounds, including unactivated ketones, using novel bulky yet flexible N-heterocyclic carbene (NHC)-coordinated 2,6-di(pentan-3-yl)aniline (IPent)-based cyclometallated palladium complexes (CYPs) as catalysts is reported. The PhS-IPent-CYP-catalyzed reactions are efficient at low catalyst loadings (0.02–0.3 mol% Pd), and the exceptional catalytic activity for 1,2-addition is attributed to the steric bulk of the NHC ligand. These reactions can yield a wide range of functionalized benzylic alcohols that are difficult to synthesize by classical protocols using highly active organomagnesium or lithium reagents.
Chiral electron-rich PNP ligand with a phospholane motif: Structural features and application in asymmetric hydrogenation
Wang, Heng,Zhang, Yao,Yang, Tilong,Guo, Xiaochong,Gong, Quan,Wen, Jialin,Zhang, Xumu
supporting information, p. 8796 - 8801 (2020/11/13)
Despite the remarkable reactivity that was achieved by a series of transition-metal catalysts with a PNP type ligand, the electron-rich chiral PNP ligands have still been rarely reported because of the difficulties in synthesis and the nature of air-sensitivity. Herein, we report a novel chiral PNP ligand (Heng-PNP) with both a rigid backbone and a bulky tert-butyl group on the phospholane motif. We successfully obtained its divalent iron complex. The chiral environment of its Ir(III) complex was also discussed with quadrant analysis. This tridentate ligand was applied in iridium-catalyzed asymmetric hydrogenation of challenging diaryl ketones: up to 98% ee and 500 TON are achieved. Computational study showed that the twist of conjugate aryl group in the substrate (induced by the special chiral pocket of Ir/Heng-PNP complex) leads to the energy difference in the enantiodetermining step.
Development of Chiral C2-Symmetric N-Heterocyclic Carbene Rh(I) Catalysts through Control of Their Steric Properties
Abadie, Marc-Antoine,Macintyre, Kirsty,Boulho, Cédric,Hoggan, Peter,Capet, Frédéric,Agbossou-Niedercorn, Francine,Michon, Christophe
supporting information, p. 536 - 543 (2019/01/14)
Chiral square-planar Rh(I) complexes based on new C2-symmetric NHC ligands have been synthesized selectively in a few steps as single diastereoisomers. These chiral precatalysts were applied to the asymmetric transfer hydrogenation of 1-phenylp
Asymmetric Hydrophosphination of Heterobicyclic Alkenes: Facile Access to Phosphine Ligands for Asymmetric Catalysis
Lu, Zhiwu,Zhang, Haoyang,Yang, Zhiping,Ding, Ning,Meng, Ling,Wang, Jun
, p. 1457 - 1463 (2019/02/01)
Asymmetric hydrophosphination is the most atomically economical and straightforward approach to the construction of chiral organophosphorus compounds. Good stereoselectivities have been achieved in asymmetric hydrophosphination of an electron-deficient C=
Access to All-Carbon Spirocycles through a Carbene and Thiourea Cocatalytic Desymmetrization Cascade Reaction
Zhuo, Shitian,Zhu, Tingshun,Zhou, Liejin,Mou, Chengli,Chai, Huifang,Lu, Yunpeng,Pan, Lutai,Jin, Zhichao,Chi, Yonggui Robin
supporting information, p. 1784 - 1788 (2019/01/14)
A new catalytic approach for rapid asymmetric access to spirocycles is disclosed. The reaction involves a carbene- and thiourea-cocatalyzed desymmetrization process with the simultaneous installation of a spirocyclic core. The use of a thiourea cocatalyst
