- Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
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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.
- Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
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- Preparation method of alkyl phosphorylated substances
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The invention discloses a preparation method of alkyl phosphorylated substances. According to the invention, alkyl carboxylic acid is used as a starting material, and raw materials are easy to obtain and are various in types. Products prepared by the method disclosed by the invention are various in types and wide in application; and a part of the products can be prepared into important phosphorus ligands and drug key intermediates through simple reduction. In addition, use of high-toxicity phosphine reagents is avoided in the method, the reaction conditions are mild, operation is simple, the yield of the target product is high, pollution is small, and the reaction operation and post-treatment processes are simple, so that the method is suitable for industrial production.
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Paragraph 0023
(2019/10/04)
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- Radical alkylphosphanylation of olefins with stannylated or silylated phosphanes and alkyl iodides
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Chemical equations presented. Intermolecular conjugate radical addition reactions of secondary and tertiary alkyl radicals derived from the corresponding alkyl iodides to activated olefins such as α,β- unsaturated esters, amides, imides, nitriles, and sulfones are described. The adduct radicals are trapped by either diphenyl(trimethylstannyl)phosphane or the commercially available diphenyl(trimethylsilyl)phosphane as chain transfer reagents to give the corresponding phosphanylated products in moderate to good yields. The overall process comprises a C-C followed by a C-P bond formation.
- Lamas, Marie-Celine,Studer, Armido
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scheme or table
p. 2236 - 2239
(2011/06/23)
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- Influence of Additions of Salts with Stable Anions on Ethyl Diphenylphosphinylacetate Alkylation
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The influence of the addition of LiClO4, Mg(ClO4)2, ans NaI, salts capable of forming complexes with electron donor centers, on the direction of Ph2P(O)CH2COOEt interphase alkylation with alkyl halides RHlg in the presence of K2CO3 and Cs2CO3 was studied.Depending on the reaction conditions mixtures with various ratios of Ph2P(O)CH2COOEt, Ph2P(O)OR, and Ph2P(O)CH2COOR were obtained upon the alkylation.The formation of these compounds can be envisioned respectively as alkylation by the methylene fragment, by phosphoryl oxygen with subsequent destruction of intermediate phosphinomethylene, and by carbonyl oxygen with further stabilization of the resulting acetal via splitting off of the lowest of the alkoxy groups.
- Yarkevich, A. N.,Smolina, E. V.,Novikova, O. V.,Tsvetkov, E. N.
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p. 553 - 558
(2007/10/03)
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- INFLUENCE OF MEDIUM ACIDITY ON THE INTERACTION OF TRIORGANYLPHOSPHINES WITH ALKYL HALIDES
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The reaction rates of triphenylphosphine with amyl chloride, and of dioctylphenylphosphine with octyl chloride, are highest in protonated media having average acidity (pKa 10-13), and they decline sharply when transferred to media with higher o
- Chauzov, V. A.,Guseva, N. N.,Kostina, L. P.
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- The Stereocontrolled Horner-Wittig Reaction: Synthesis of Disubstituted Alkenes
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Addition of the lithium derivatives of phosphine oxides Ph2P(O)CH2R1 to aldehydes gives erythro adducts (11) with good stereoselectivity.Reduction of α-diphenylphosphinoyl ketones (12) gives threo adducts (11) with even better stereoselectivity.Purification by flash chromatography and/or crystallisation followed by elimination of Ph2PO2 gives pure Z- or E-alkenes with high material conversion.Explanations are offered for the stereoselectivities, conditions defined for full stereochemical control, and guidelines suggested for approaches to a given alkene.
- Buss, Antony D.,Warren, Stuart
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p. 2307 - 2326
(2007/10/02)
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- CIS-OLEFINS FROM THE HORNER-WITTIG REACTION; ORIGIN AND OPTIMISATION OF STEREOCHEMISTRY
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Conditions are described to produce high yields of erythro Horner-Wittig intermediates: stereospecific elimination gives cis-alkenes.
- Buss, Antony D.,Warren, Stuart
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p. 3931 - 3934
(2007/10/02)
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