80326-98-3Relevant academic research and scientific papers
Organic phosphorus ligand as well as preparation method and application thereof
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Paragraph 0087-0094, (2022/01/10)
The invention provides a novel phosphine ligand and a preparation method thereof. Fuel ethanol can be obtained from a mixture of synthetic gas and methanol through a one-pot method under the condition that a phosphine ligand and an Rh/Ru bimetallic catalyst precursor are mixed. Through process optimization, the reaction can be carried out under mild conditions, the selectivity is high, and the cost can be greatly reduced. The novel phosphine ligand has good industrialization prospects and huge economic benefits and social values.
Gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation
Aitipamula, Srinivasulu,Britovsek, George J. P.,Nobbs, James D.,Romain, Charles,Tay, Dillon W. P.,Van Meurs, Martin,White, Andrew J. P.
, p. 663 - 671 (2020/01/02)
A series of palladium complexes with C3-bridged bidentate bis(diphenylphosphino)propane ligands with substituents of varying steric bulk at the central carbon have been synthesized. The size of the gem-dialkyl substituents affects the C-C-C bond angles within the ligands and consequently the P-M-P ligand bite angles. A combination of solid-state X-ray diffraction (XRD) and density functional theory (DFT) studies has shown that an increase in substituent size results in a distortion of the 6-membered metal-ligand chair conformation toward a boat conformation, to avoid bond angle strain. The influence of the gem-dialkyl effect on the catalytic performance of the complexes in palladium-catalyzed hydroformylation of 1-octene has been investigated. While hydroformylation activity to nonanal decreases with increasing size of the gem-dialkyl substituents, a change in chemoselectivity toward nonanol via reductive hydroformylation is observed.
Decarboxylative Phosphine Synthesis: Insights into the Catalytic, Autocatalytic, and Inhibitory Roles of Additives and Intermediates
Jin, Shengfei,Haug, Graham C.,Nguyen, Vu T.,Flores-Hansen, Carsten,Arman, Hadi D.,Larionov, Oleg V.
, p. 9764 - 9774 (2019/10/14)
Phosphines are among the most widely used ligands, catalysts, and reagents. Current synthetic approaches to phosphines are dominated by nucleophilic displacement reactions with organometallic reagents. Here, we report a radical-based approach to phosphines that proceeds by a cross-electrophile coupling of chlorophosphines and redox-active esters. The reaction allows for the synthesis of a broad range of substituted phosphines that were not readily attainable with the present methods. Our experimental and DFT computational studies also clarified the catalytic, autocatalytic, and inhibitory roles of additives and intermediates, as well as the mechanistic details of the photocatalytic and zinc-mediated redox modes that can have implications for the mechanistic interpretation of other cross-electrophile coupling reactions.
Thorpe–Ingold Effect in Branch-Selective Alkylation of Unactivated Aryl Fluorides
O'Neill, Matthew J.,Riesebeck, Tim,Cornella, Josep
, p. 9103 - 9107 (2018/07/24)
Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C?C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron-rich and electron-deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites.
METHOD FOR PRODUCING TERTIARY PHOSPHINES
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Page/Page column 21, (2008/06/13)
The invention relates to a method for producing tertiary phosphines by reacting a compound of general formula (I) with (a) an alkali metal in an organic aprotic solvent and (b) a compound of general formula (II). In formula (I), A represents R1 or L2, B represents R2 or L3, where the groups R1 and R2 independently of one another stand for an organic group with respectively between 1 and 30 carbon atoms and said groups R1 and R2 can also be bonded together. The leaving groups L1 to L3 independently of one another represent halogen, alkyloxy with between 1 and 10 carbon atoms or aryloxy with between 6 and 10 carbon atoms. In formula (II), the group R3 represents an organic group with respectively between 1 and 30 carbon atoms and the leaving group L4 represents halogen, alkyloxy with between 1 and 10 carbon atoms or aryloxy with between 6 and 10 carbon atoms. The reaction mixture that is obtained is hydrolysed using an aqueous base with a pH value of > 10 and the organic phase is then separated from the aqueous phase.
