36838-04-7Relevant articles and documents
The phosphinoboration of acyl chlorides
Binder, Justin F.,Geier, Stephen J.,Lafortune, James H. W.,Macdonald, Charles L. B.,Murphy, Maia C.,Stephan, Douglas W.,Trofimova, Alina,Vogels, Christopher M.,Westcott, Stephen A.
, p. 5092 - 5099 (2020)
This investigation examines the reactivity of phosphinoboronate esters Ph2PBpin (pin = 1,2-O2C2Me4) and Ph2PBcat (cat = 1,2-O2C6H4), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR′2 along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the CO double bond at elevated temperatures to give the corresponding diphosphines RC(OBR′′2)(PR′2)2. These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh2)2 (2a) with (η5-C9H7)Rh(η2-coe)2 (coe = cis-cyclooctene) affording the indenyl rhodium complex (η5-C9H7)Rh(PhC(OBpin)(PPh2)2) (3a) where the phosphines are bound to the metal centre in a κ2-P,P bidentate manner.
Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
supporting information, (2020/06/29)
Palladium-catalyzed C(sp3)–P(III) bond formation reaction for alkyl substituted phosphines preparation was developed. In this reaction, various alkyl bromides and limited alkyl chlorides reacted with acylphosphine under relative mild and easily accessible condition, and differential phosphines were afforded in good yields. This reaction made up the application of palladium catalysis in C(sp3)–P(III) bond formation, and indicated a practical application of acylphosphine as a phosphination reagent.
Continuous preparation method of trimethylbenzoyl-diphenylphosphine oxide compound
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Paragraph 0035-0036, (2019/10/07)
The invention discloses a continuous preparation method of trimethylbenzoyl-diphenylphosphine oxide (TPO) and its derivatives. The preparation method comprises: in a tubular reactor, benzaldehyde or its derivative reacts with chlorodiphenyl phosphine or its derivative; and then a catalytic oxidation reaction is directly carried out without separation, and the reaction solution is desolvated and re-crystallized to obtain a TPO product. The conversion rate of the product TPO is 98% and above, and the finished product content reaches 99.5% and above.
The effect of an acylphosphine ligand on the rhodium-catalyzed hydrosilylation of alkenes
Li, Jiayun,Yang, Chuang,Bai, Ying,Yang, Xiaoling,Liu, Yu,Peng, Jiajian
, p. 7 - 11 (2018/01/01)
We synthesized a series of acylphosphines and investigated the hydrosilylation of alkenes that were catalyzed using RhCl3/acylphosphine. The results indicated that RhCl3/(diphenylphosphino) (phenyl)methanone exhibited higher activity as well as higher levels of β–adduct selectivity.
Differentially Substituted Phosphines via Decarbonylation of Acylphosphines
Yu, Rongrong,Chen, Xingyu,Martin, Stephen F.,Wang, Zhiqian
, p. 1808 - 1811 (2017/04/11)
A new route to phosphines was developed by a method that features a "pre-join and transform" process that proceeds via acylphosphine intermediates that may be readily prepared from carboxylic acids and disubstituted phosphines. The efficient decarbonylations of these acylphosphines using a nickel catalyst delivered the corresponding phosphines. This method shows that the carboxyl group can play a role similar to halides or triflates for introducing a substituted phosphorus atom on an aromatic ring.
Palladium-catalyzed C–P(III) bond formation reaction with acylphosphines as phosphorus source
Yu, Rongrong,Chen, Xingyu,Wang, Zhiqian
supporting information, p. 3404 - 3406 (2016/07/11)
Palladium-catalyzed C–P(III) bond formation reaction employing acylphosphines as the phosphorus source was developed. Under the optimized conditions, acylphosphines could react with aryl halides directly affording trivalent phosphines in up to 94% yield.
The carbonyl group tuned electron-deficient phosphorus ligands and their application in Rhodium catalyzed arylation to aldehydes
Yang, Jiefang,Chen, Xingyu,Wang, Zhiqian
supporting information, p. 5673 - 5675 (2015/09/15)
Acylphosphines, which could be efficiently prepared from acid chlorides and secondary phosphines, were developed as a type of carbonyl group tuned electron-deficient phosphorus ligand. They were found to be a kind of efficient ligand in Rhodium catalyzed arylation to aldehydes through accelerating the transmetalation process. Chiral acylphosphine ligands could be generated from carboxylic acids bearing the chiral framework correspondingly.
Asymmetric synthesis of α-chiral hydroxyalkylphosphines by a catalytic enantioselective reduction of acylphosphines
Hayashi, Minoru,Ishitobi, Hiroyuki,Matsuura, Yutaka,Matsuura, Takashi,Watanabe, Yutaka
supporting information, p. 5830 - 5833 (2015/01/16)
Enantioselective reduction of acylphosphines, after precomplexation with borane, proceeded smoothly in the presence of a chiral oxazaborolidine catalyst and catecholborane. α-Hydroxyalkylphosphine products were obtained as phosphine-borane complexes in good yield and enantioselectivity. One of the products of the enantioselective reduction was successfully applied as an optically active phosphine ligand for asymmetric catalysis after suitable derivatization.
ORGANISCHE PHOTOCHEMIE XXXII Beitrag ueber Photoreaktionen von Aroyl-diphenylphosphinen in Loesung
Dankowski, Manfred,Praefcke, Klaus
, p. 105 - 108 (2007/10/02)
Three new examples to photoreactions of aroyl diphenyl phosphines which undergo α-cleavage as well as 1,2-oxygen transfer from the carbonyl group onto the phosphorous atom are described.Both reactions also occur in the mass spectrometer.
