Raney-Ni reduction of phosphine sulfides

Demchuk, Oleg M.; Świerczyńska, Wioletta; Dziuba, Kamil; Frynas, Sławomir; Flis, Anna; Pietrusiewicz, K. Michał

doi:10.1080/10426507.2016.1225052

Cited by 7 publications

(6 citation statements)

References 27 publications

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“…After an extensive survey, most of the reported phosphine oxide reduction methods were not successful . Alternatively, the chiral StackPhos sulfide 14k was successfully reduced with Raney-Ni to give the product without any loss of enantiopurity at room temperature (see SI for full details) . While this strategy worked well, it should be noted that lower enantioselectivities were obtained when other phosphine sulfides were exposed to the enantioselective phase-transfer catalysis reaction, and hence, we were resolute in identifying more widely applicable PO reduction conditions.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Enantioselective Synthesis of Axially Chiral Imidazoles by Cation-Directed Desymmetrization

Yin,

Liu,

Weeks

et al. 2023

J. Am. Chem. Soc.

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Section: Resultsmentioning

confidence: 99%

Catalytic Enantioselective Synthesis of Axially Chiral Imidazoles by Cation-Directed Desymmetrization

Yin,

Liu,

Weeks

et al. 2023

J. Am. Chem. Soc.

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“…The MeOSym-Phos ligand (1) was obtained from inexpensive starting materials by a synthetic protocol similar to that reported previously [2]. The phosphine sulfide MeOSym-PhosS (5) was next subjected to a desulfuration reaction by treatment with Ni-Raney reagent [21] to give ligand 1 in an almost quantitative yield (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

A Single Biaryl Monophosphine Ligand Motif—The Multiverse of Coordination Modes

Miroslaw,

Dybala,

Jasiński

et al. 2023

Inorganics

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Biaryl monophosphines are important precursors to active catalysts of palladium-mediated cross-coupling reactions. The efficiency of the phosphine-based transition metal complex catalyst has its origin in the electronic structure of the complex used and the sterical hindrance created by the ligand at an active catalyst site. The aim of this paper is to shed some light on the multiverse of coordination modes of biaryl monophosphine ligands. Here, we present the analysis of the X-ray single crystal structures of palladium(II) complexes of a family of biaryl monophosphine ligands and the first crystallographic report on a related phosphine sulfide. Despite the common biaryl monophosphine ligand motif, they show diverse coordination modes (i) starting from the activation of aromatic C atoms and producing a C,P metallacycle, through (ii) the O,P chelation to Pd(II) ions with a simultaneous demethylation reaction of one of the methoxy groups, ending up with (iii) the monodentate coordination to metal cations via P atoms or (iv) via S atoms in the case of phosphine sulfide. We relate our results to the crystal structures found in the Cambridge Structural Database to show the multiverse of coordination modes in the group of biaryl monophosphine ligands.

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“…In continuation of our studies in the field of synthesis and application of tertiary phosphine ligands [40][41][42][43][44][45][46][47][48], herein we present a new method of deprotection of phosphines from corresponding borane complexes. The main aim of our studies is to present a simple and inexpensive synthetic approach leading to sensitive target phosphines with high purities and high yields with no need to apply post reaction purification.…”

Section: Resultsmentioning

confidence: 99%

“…c borane complex was prepared according to known procedure [32,66] >92 % ee substrate was used, >90 % ee product was obtained (borane complex: HPLC, Chiralcel ad-h column; phosphine converted to oxide: 1 H, 31 P NMR in the presence of Naproxen) [62]. d borane complex was prepared according to known procedure [40,63] Conditions: 60 °C, 18 h, 2 equiv. Me 3 P, 48 % de substrate was used, 46 % de product was obtained ( 1 H, 31 P NMR).…”

Section: (99)mentioning

confidence: 99%

A clean and simple method for deprotection of phosphines from borane complexes

Demchuk

Jasiński

Strzelecka

et al. 2017

Pure and Applied Chemistry

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Simple, efficient, clean, and stereospecific protocols of protection of phosphorus atom with borane and deprotection from the borane complexes of the tertiary phosphines in mild conditions are reported. The proposed protection/deprotection reactions tolerate a range of functional groups and lead to pure products with excellent yield with no need for application of chromatographic or crystallisation purification procedures. For the first time mechanisms of the reactions of phosphine protection and deprotection have been studied based on experimental kinetic data as well as quantumchemical calculations, which allows designing reaction conditions suitable for a given substrate.

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Raney-Ni reduction of phosphine sulfides

Cited by 7 publications

References 27 publications

Catalytic Enantioselective Synthesis of Axially Chiral Imidazoles by Cation-Directed Desymmetrization

Catalytic Enantioselective Synthesis of Axially Chiral Imidazoles by Cation-Directed Desymmetrization

A Single Biaryl Monophosphine Ligand Motif—The Multiverse of Coordination Modes

A clean and simple method for deprotection of phosphines from borane complexes

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