53111-20-9Relevant academic research and scientific papers
A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
Taylor, Nicholas P.,Gonzalez, Jorge A.,Nichol, Gary S.,García-Domínguez, Andrés,Leach, Andrew G.,Lloyd-Jones, Guy C.
supporting information, p. 721 - 729 (2022/01/04)
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
supporting information, p. 16374 - 16382 (2020/11/03)
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
Novel neutral monodentate chelated manganese complex as well as preparation method and application thereof
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Paragraph 0048-0052, (2020/10/20)
The invention discloses a novel neutral monodentate chelated manganese complex. Different electron donating and withdrawing substituents, such as N (Me) 2, OMe, CF3, OCF3, Cl, F, CN and Br, are introduced to a triphenylphosphine oxide ligand, so that the emission energy level and the luminescence life of the manganese complex can be easily adjusted, and the luminescence property of a material is further changed; and besides, information storage and protection can be realized by utilizing the neutral manganese complex.
A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine
Xu, Zhaotao,Wang, Pingping,Chen, Qiurong,Cai, Mingzhong
, p. 50 - 58 (2018/04/23)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in DMAc at 130 °C in the presence of 1.0 mol% of MCM-41-supported tridentate nitrogen palladium(0) complex [MCM-41-3N-Pd(0)] with KOAc as base, yielding a variety of unsymmetrical triarylphosphines in good to excellent yields. The turnover frequency (TOF) of the catalyst can reach 30.67 h?1. This new heterogeneous palladium(0) catalyst could easily be prepared by a simple procedure from commercially readily available reagents, and exhibited the same catalytic activity as homogeneous Pd(OAc)2 or Pd(PPh3)4, and could be recovered by filtration of the reaction solution and recycled at least seven times without significant loss of catalytic activity.
An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
, (2018/07/31)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
Organocatalyzed Reduction of Tertiary Phosphine Oxides
Schirmer, Marie-Luis,Jopp, Stefan,Holz, Jens,Spannenberg, Anke,Werner, Thomas
supporting information, p. 26 - 29 (2016/01/25)
A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.
Rhodium-Catalyzed Double Alkyl-Oxygen Bond Cleavage: An Alkyl Transfer Reaction from Bis/Tris(o-alkyloxyphenyl)phosphine to Aryl Acids
Zhou, Hui,Zhang, Jinlong,Yang, Huameng,Xia, Chungu,Jiang, Gaoxi
supporting information, p. 3406 - 3412 (2016/10/21)
An unprecedented rhodium-catalyzed selective cleavage of double alkyl-oxygen bonds of bis/tris(o-alkyloxyphenyl)phosphine has been realized, in which P atom functions as a directing group and simple aryl acids are the methyl group acceptor to provide methyl esters and a quaternary phosphonium salt. The preliminary mechanism was investigated via an 18O labeling experiment and stoichiometric reaction between a Rh-A crystal and an aromatic acid.
Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene
Xue, Mei,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
, p. 120 - 126 (2014/02/14)
A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.
Discovery of a robust and efficient homogeneous silver(I) catalyst for the cycloaddition of azides onto terminal alkynes
McNulty, James,Keskar, Kunal
, p. 5462 - 5470 (2012/10/30)
A highly efficient, chemically stable, and well-defined homogeneous silver(I) catalyst is reported for the cycloaddition of azides onto terminal alkynes (Ag-AAC reaction). The Ag-AAC reaction occurs at room temperature or with heating to deliver exclusive
Deprotonative metalation of substituted aromatics using mixed lithium-cobalt combinations
Dayaker, Gandrath,Chevallier, Floris,Gros, Philippe C.,Mongin, Florence
experimental part, p. 8904 - 8910 (2011/01/04)
The deprotonation of anisole was attempted using different homo- and heteroleptic TMP/Bu mixed lithium-cobalt combinations. Using iodine to intercept the metalated anisole, an optimization of the reaction conditions showed that in THF at room temperature 2 equiv of base were required to suppress the formation of the corresponding 2,2′-dimer. The origin of the dimer was not identified, but its formation was favored with allyl bromide as electrophile. The metalated anisole was efficiently trapped using iodine, anisaldehyde, and chlorodiphenylphosphine, and moderately employing benzophenone, and benzoyl chloride. 1,2-, 1,3-, and 1,4-dimethoxybenzene were similarly converted regioselectively to the corresponding iodides. It was observed that 2-methoxy- and 2,6-dimethoxypyridine were more prone to dimerization than the corresponding benzenes when treated similarly. Involving ethyl benzoate in the metalation-iodination sequence showed that the method was not suitable to functionalize substrates bearing reactive functions.
