Chiral phosphine-phosphoramidite ligands in asymmetric catalysis

Chen, Xiu-Shuai; Hou, Chuan-Jin; Hu, Xiang‐Ping

doi:10.1080/00397911.2016.1171362

Cited by 20 publications

(4 citation statements)

References 53 publications

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“…Guided by these reports, we anticipated that the best way to manipulate the reactivity of 1 would be to offer a competitive ligand to replace carbonyls and activate 1 in situ . Phosphorus ligands such as phosphines, phosphites, phosphinites, diphosphines, diphosphites, phosphine-phosphonite, phosphine-phosphoramidite and phosphine-phosphite have been extensively utilized in rhodium catalyzed hydroformylation. Thus, given the success of the phosphorus ligand in hydroformylation, we zeroed in on readily accessible σ-donor ligands such as phosphines and σ-donor π-acceptor ligands such as phosphites .…”

Section: Resultsmentioning

confidence: 99%

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

et al. 2018

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Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)][PhPNPPh] (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4- iBu-styrene (S13), 4- tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [HFe(CO)(PPh)] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.

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Section: Resultsmentioning

confidence: 99%

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

et al. 2018

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“…Since Pasteur manually separated, under the microscope with pliers, sodium ammonium tartrate enantiomers through their crystalline form in 1848 [1], several methods have been developed, such as asymmetric synthesis, kinetic resolution of racemates or chiral chromatography [2][3][4][5]. For this last possibility, one of the preferred methodologies is asymmetry catalysis [6-8], using, for example, as a chiral agent, phosphines [9][10][11][12][13][14][15][16][17][18][19] or N-heterocyclic carbenes [20][21][22] ligands associated with a transition metal, such as ruthenium [23][24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

How an Internal Supramolecular Interaction Determines the Stereochemistry of a Metal Center

Steinmetz,

Gourlaouen,

Sémeril

2024

Organics

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The chloro-P,N-{diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-me- thyl]}(p-cymene)ruthenium(II) hexafluorophosphate complex (4) was obtained in two steps from diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-methyl] borane (2). In the first step, the oxadiazole ring coordinated with the ruthenium atom, resulting in the formation of the dichloro-N-{diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-methyl]borane}(p-cymene) ruthenium(II) complex (3). During the crystallization of the P,N-chelate ruthenium complex, the formation of conglomerate crystals was revealed by X-ray structure analysis. Only two stereoisomers were obtained with (S)-Ru and (R)-C configurations in the first complex and with (R)-Ru and (S)-C configurations in the second. This deracemization during crystallization is due to the formation of a hydrogen bond between the P,N-ligand and the chlorine atom (CH•••Cl). This supramolecular interaction allows the transfer of the ligand chirality to the metal center and decrees the stereochemistry of the ruthenium atom.

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“…Compounds with a phosphorus atom attached to a stereogenic carbon center in acyclic and cyclic structures play an important role as chiral ligands in transition metal complexes [2]. They were applied to various catalytic asymmetric reactions [3–4], such as hydrogenations [3–6], conjugated additions to enones [7], and allylic alkylations [8–9]. Another direction of research is the use of phosphines in organocatalysis [10–11] and bifunctional catalysis [12].…”

Section: Introductionmentioning

confidence: 99%

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene

Kmieciak¹,

Krzemiński²

2019

Beilstein J. Org. Chem.

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New chiral regioisomeric γ-hydroxyphosphine ligands were synthesized from α-pinene. The key transformation was the thermal [2,3]-sigmatropic rearrangement of allyldiphenylphosphinites, obtained from (1R,2R,4S,5R)-3-methyleneneoisoverbanol and (1R,2R,3R,5R)-4-methyleneneoisopinocampheol, to allylphosphine oxides. Hydroxy groups were introduced stereoselectively through a hydroboration–oxidation reaction proceeding from the less hindered site providing a trans relationship between the hydroxy and the phosphine substituents.

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Chiral phosphine-phosphoramidite ligands in asymmetric catalysis

Cited by 20 publications

References 53 publications

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process

How an Internal Supramolecular Interaction Determines the Stereochemistry of a Metal Center

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene

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