- Novel Direct Deoxygenation of the Hydroxy Group of (1-Hydroxyalkyl)-diphenylphosphine Oxides
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The hydroxyl group of (1-hydroxyalkyl)-diphenylphosphine oxides 1 is directly deoxygenated on treatment with phosphorus trichloride and iodides to give parent alkyl-diphenylphosphine oxides 2.
- Yamashita, Mitsuji,Suzuki, Takanobu,Imoto, Hiroyuki,Oshikawa, Tatsuo,Inokawa, Saburo
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- Correlation of the rates of solvolysis of chlorodiphenylphosphine using the extended grunwald-winstein equation
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Specific rates of solvolysis involving displacement of chloride from the trivalent phosphorus of chlorodiphenylphosphine (Ph2PCl, 1) are reported for ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The 25 solvents give an extended Grunwald-Winstein correlation with an l value of 1.25 0.09, m value of 0.46 0.06, and correlation coefficient (R) of 0.954. The reactions in aqueous acetone were unusually fast, and these data points lie above the plot. Specific rate values are also reported for TFE-ethanol mixtures. For five representative solvents, values were obtained at three additional temperatures and activation parameters are presented. Rather low enthalpies of activation (8.4 to 11.8 kcal mol-1) are accompanied by very negative entropies of activation (-33 to -46 cal mol-1K-1). The kinetic features observed are consistent with an SN2 reaction incorporating appreciable bond formation and bond breaking at the transition state, and they are very similar to those previously observed for diphenylphosphinyl chloride (Ph2POCl).
- Koh, Han Joong,Kevill, Dennis N.
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- METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0050; 0079
(2020/05/02)
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- Bipyridine structure ligand and preparation method thereof, bipyridine structure-based catalytic system and application of bipyridine structure-based catalytic system in ethylene oligomerization
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The invention provides a bipyridine structure ligand represented by a formula I and a preparation method thereof, and the invention also provides a catalytic system based on the bipyridine structure and an application of the catalytic system in ethylene oligomerization, wherein the catalytic system comprises the bipyridine structure ligand, a metal precursor taking chromium as a center and a cocatalyst. The catalytic system can improve the selectivity of 1-octene and greatly reduce oligomers in ethylene oligomerization reaction, the selectivity of the 1-octene is 79.2%, the content of the oligomer is 0.8%, and possibility is provided for ethylene oligomerization industrialization.
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Paragraph 0103; 0106
(2020/07/15)
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- Synthesis method of trisubstituted phosphine oxide compound
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The invention provides a synthesis method of a trisubstituted phosphine oxide compound. In the method, monohydric alcohol or dihydric alcohol which is inexpensive, readily available, stable and low intoxicity are used as alkylating agents, and cheap and readily available halosilane is used as a catalyst, thus directly obtaining the trisubstituted phosphine oxide compound through high-selectivityreaction. The reaction method is simple, the conditions are mild, no solvent is needed, the operation is easy, and water is a reaction by-product. The method has low requirements on the reaction conditions, and benzyl type, allyl type and aliphatic type alcohol can be used as the alkylating agent to realize the synthesis of the target phosphine oxide compound, and has a relatively wide applicationrange. The method can also conveniently scale up the production by 20 times and carry out the gram-level preparation of products, so the method should also have certain research and industrial application prospects.
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Paragraph 0030
(2019/05/08)
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- Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
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Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
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supporting information
p. 2916 - 2922
(2019/06/18)
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- Direct C-OH/P(O)-H dehydration coupling forming phosphine oxides
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A t-BuONa-mediated C-OH/P(O)-H cross dehydration coupling to produce alkylphosphine oxides is developed. This reaction employed readily available alcohols and P(O)-H compounds as the starting materials, providing an efficient alternative method for constructing sp3 C-P bonds. A reasonable reaction path involving dehydration and subsequent regio-selective hydrophosphorylation of the resulting alkenes was proposed.
- Chen, Long,Zhu, Yueyue,Chen, Tieqiao,Liu, Long,Zhang, Ji-Shu,Han, Li-Biao
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supporting information
p. 5090 - 5093
(2018/07/29)
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- Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
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Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
- Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
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supporting information
p. 11530 - 11536
(2018/09/21)
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- Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization
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A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway.
- Lhermet, Rudy,Moser, Emile,Jeanneau, Erwann,Olivier-Bourbigou, Hélène,Breuil, Pierre-Alain R.
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supporting information
p. 7433 - 7437
(2017/06/06)
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- Practical way for the synthesis of phosphine oxides and phosphine sulfides from benzyl alcohol derivatives
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The reaction of benzyl alcohol derivatives with Ph2PI generated in situ from Ph2PCl and NaI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to excellent yields.
- Ma, Yutao,Chen, Feng,Bao, Jifeng,Wei, Hao,Shi, Min,Wang, Feijun
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supporting information
p. 2465 - 2467
(2016/05/24)
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- The Mechanism of Phosphonium Ylide Alcoholysis and Hydrolysis: Concerted Addition of the O?H Bond Across the P=C Bond
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The previous work on the hydrolysis and alcoholysis reactions of phosphonium ylides is summarized and reviewed in the context of their currently accepted mechanisms. Several experimental facts relating to ylide hydrolysis and to salt and ylide alcoholysis are shown to conflict with those mechanisms. In particular, we demonstrate that the pKavalues of water and alcohols are too high in organic media to bring about protonation of ylide. Therefore, we propose concerted addition of the water or alcohol O?H bond across the ylide P=C bond. In support of this, we provide NMR spectroscopic evidence for equilibrium between ylide and aclohol that does not require the involvement of phosphonium hydroxide. We report the first P-alkoxyphosphorane to be characterised by NMR spectroscopy that does not undergo exchange on an NMR timescale. Two-dimensional NMR spectroscopic techniques have been applied to the characterisation to P-alkoxyphosphoranes for the first time.
- Byrne, Peter A.,Gilheany, Declan G.
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supporting information
p. 9140 - 9154
(2016/07/14)
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- Organic photoredox catalysis for the oxidation of silicates: Applications in radical synthesis and dual catalysis
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Metal free photooxidation of alkyl bis(catecholato)silicates with the organic dye 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano-benzene (4CzIPN) allows the smooth formation of alkyl radicals. The latter can be efficiently engaged either with radical acceptors to provide homolytic addition products or in photoredox/nickel dual catalysis reactions to obtain cross-coupling products.
- Lévêque, Christophe,Chenneberg, Ludwig,Corcé, Vincent,Ollivier, Cyril,Fensterbank, Louis
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p. 9877 - 9880
(2016/08/11)
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- Aryl group - A leaving group in arylphosphine oxides
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The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when treated with organolithium reagent.
- Stankevi?, Marek,Pisklak, Jolanta,W?odarczyk, Katarzyna
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p. 810 - 824
(2016/01/20)
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- Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides
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We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs. This journal is the Partner Organisations 2014.
- Fu, Tingting,Qiao, Hongwei,Peng, Zhimin,Hu, Gaobo,Wu, Xueji,Gao, Yuxing,Zhao, Yufen
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p. 2895 - 2902
(2014/05/06)
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- Nickel-catalyzed C-P cross-coupling of arylboronic acids with P(O)H compounds
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A novel and efficient Ni-catalyzed coupling of a wide range of arylboronic acids with H-phosphites, H-phosphinate esters, and H-phosphine oxides has been developed, providing a general and powerful tool for the synthesis of various aryl-phosphorus compounds, especially for valuable triarylphosphine oxides, in good to excellent yield. This protocol is the first Ni-catalyzed C-P bond-forming reaction between arylboronic acids and P(O)H compounds.
- Hu, Gaobo,Chen, Weizhu,Fu, Tingting,Peng, Zhimin,Qiao, Hongwei,Gao, Yuxing,Zhao, Yufen
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supporting information
p. 5362 - 5365
(2013/11/06)
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- Copper-catalyzed P-arylation via direct coupling of diaryliodonium salts with phosphorus nucleophiles at room temperature
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A new method for copper-catalyzed P-C bond formation through reaction of phosphorus nucleophiles with diaryliodonium salts at room temperature is described. Most target products are obtained with this method in high yields within a short reaction time of 10 min. It can be easily adapted to large-scale preparations. When unsymmetrical iodonium salts are employed, nucleophilic substitution occurs preferentially on the sterically hindered aromatic ring or the more electron-deficient ring.
- Xu, Jian,Zhang, Pengbo,Gao, Yuzhen,Chen, Yiyin,Tang, Guo,Zhao, Yufen
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p. 8176 - 8183
(2013/09/12)
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- Lewis acid catalyzed room-temperature Michaelis-Arbuzov rearrangement
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The taming of the shrew! For the first time, a broadly applicable efficient room-temperature Arbuzov rearrangement is described. This reaction is accomplished through an atom-economical Lewis acid catalyzed process (see scheme, TMSOTf=trimethylsilyl trifluoromethane-sulfonate). The method has been generalized to primary and activated secondary phosphites, phosphinites, and phosphonites.
- Renard, Pierre-Yves,Vayron, Philippe,Leclerc, Eric,Valleix, Alain,Mioskowski, Charles
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p. 2389 - 2392
(2007/10/03)
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- Trimethylsilyl halide-promoted Michaelis-Arbuzov rearrangement
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(Matrix presented) We describe a new, straightforward, and easy-to-handle method for achieving an unprecedented trimethylsilyl halide-catalyzed Michaelis-Arbuzov-like rearrangement. This rearrangement occurs at temperatures from room temperature to 80°C and does not require addition of any alkyl halide. The scope and limitations of this new reaction are explored, as well as its mechanism.
- Renard, Pierre-Yves,Vayron, Philippe,Mioskowski, Charles
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p. 1661 - 1664
(2007/10/03)
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- Mechanisms of hydrogen-, oxygen-, and electron-transfer reactions of cumylperoxyl radical
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Rates of hydrogen-transfer reactions from a series of para-substituted N,N-dimethylanilines to cumylperoxyl radical and oxygen-transfer reactions from cumylperoxyl radical to a series of sulfides and phosphines have been determined in propionitrile (EtCN) and pentane at low temperatures by use of ESR. The observed rate constants exhibit first-order and second-order dependence with respect to concentrations of N,N-dimethylanilines. This indicates that the hydrogen- and oxygen-transfer reactions proceed via 1:1 charge-transfer (CT) complexes formed between the substrates and cumylperoxyl radical. The primary kinetic isotope effects are determined by comparing the rates of N,N-dimethylanilines and the corresponding N,N-bis(trideuteriomethyl)anilines. The isotope effect profiles are quite different from those reported for the P-450 model oxidation of the same series of substrates. Rates of electron-transfer reactions from ferrocene derivatives to cumylperoxyl radical have also been determined by use of ESR. The catalytic effects of Sc(OTf)3 (OTf = triflate) on the electron-transfer reactions are compared with those of Sc(OTf)3 on the hydrogen- and oxygen-transfer reactions. Such comparison provides strong evidence that the hydrogen- and oxygen- transfer reactions of cumylperoxyl radical proceed via a one-step hydrogen atom and oxygen atom transfer rather than via an electron transfer from substrates to cumylperoxyl radical.
- Fukuzumi, Shunichi,Shimoosako, Kanji,Suenobu, Tomoyoshi,Watanabe, Yoshihito
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p. 9074 - 9082
(2007/10/03)
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- Convenient method for the reduction of the double-bond of cyclic vinylphosphine oxides using borane
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The electronpoor double-bond of cyclic vinylphosphine oxides (1, 3 and 4) is easily reduced by borane in a selective manner to give the corresponding saturated derivatives (2, 4 and 5, respectively) Under forcing conditions, change of the functionality may also take place.
- Keglevich,Fekete,Chuluunbaatar,Dobo,Bocskei,Toke
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p. 4221 - 4231
(2007/10/03)
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- A novel carbon leaving group in the reaction of organometallic compounds with phosphine oxides
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The reaction of diphenyl(methoxymethyl)phosphine oxide 1 with organometallic reagents was found to lead to substitution of the methoxymethyl group. The P-phenyl substituent showed a lower propensity to undergo a displacement.
- Cardellicchio, Cosimo,Fracchiolla, Giuseppe,Naso, Francesco,Tortorella, Paolo,Holody, Wieslawa,Michal Pietrusiewicz
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p. 5773 - 5776
(2007/10/03)
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- Solvolysis of phosphonium compounds containing a thiophenoxy group linked to phosphorus
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A kinetic study of the solvolysis of six alkylphenyl thiophenoxyphosphonium chlorides in 50% water/ methanol is reported. The rates of solvolysis, where thiophenol and phosphine oxides are formed, are little influenced by the substituents linked to phosphorus. The present findings are in sharp contrast to the 104 higher rate of the alkaline decomposition of tetraphenyl as compared to trialkylphenyl phosphonium salts, where phenyl is the leaving group. Further, the rate of solvolysis of the cyclic phenyl thiophenoxyphospholanium salt, is nearly identical to the rate of the corresponding dialkylphenyl thiophenoxyphosphonium compound. Calculation of the activation parameters of the solvolysis of thiophenoxyphosphonium compounds shows that the underlying reaction forces, expressed as activation energies and entropies, are strongly influenced by the substituents. The results suggest that the thiophenoxy group is expelled from the pentacovalent, trigonal bipyramidal reaction intermediate, before pseudorotation of the substituents linked to phosphorus takes place.
- Aksnes, Gunnar
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- Reactions of (1-Chlorovinyl)diphenylphosphine Oxide with Organometallic Reagents
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Direct substitution of 1-chlorovinyl group by an aryl or an alkyl group in the reactions of (1-chlorovinyl)diphenylphosphine oxide with aryl and alkyl Grignard reagents was observed, whereas in its reactions with the corresponding cuprates addition across the double bond constituted the dominant reaction pathway.
- Cardellicchio, Cosimo,Fiandanese, Vito,Naso, Francesco,Pietrusiewicz, K. Michal,Wisniewski, Witold
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p. 3135 - 3138
(2007/10/02)
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- REACTIONS OF PHOSPHONOUS ACIDS WITH TRIETHYLALUMINUM
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The reaction of triethylaluminum with phosphonous acids proceeds via adduct formation, by coordination of aluminum with phosphonous oxygen. At higher temperature the adduct is converted to a P-O-Al system with evolution of ethane, and to complexes of tertiary phosphine oxides with diethylaluminum hydride. The latter form by isomerization, described here for the first time.
- Nifant'ev, E. E.,Trofimtsova, I. A.,Chekulaeva, L. A.,Chechegoeva, E. V.,Gavrilenko, V. V.
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p. 841 - 844
(2007/10/02)
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- Group 6 anionic ·-hydride complexes [HM2(CO)10]- (M = Cr, Mo, W): New catalysts for hydrogenation and hydrosilylation
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Group 6 anionic ·-hydride complexes catalyze hydrogenation of conjugated olefins, aldehydes, ketoesters, and alkynes, and hydrosilylation of aldehydes and conjugated olefins with high regio- and stereoselectivity. Ketones are converted into silyl ethers and silyl enol ethers with monohydrosilanes and dihydrosilanes, respectively.
- Fuchikami, Takamasa,Ubukata, Yumiko,Tanaka, Yasutaka
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p. 1199 - 1202
(2007/10/02)
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- Photochemical Anion-Promoted Carbon-Sulfur Cleavage Reactions of Diaryl Sulfides, Alkyl Aryl Sulfides, and Related Sulfoxides and Sulfones
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Diaryl sulfides and the related sulfoxides and sulfones react with substances such as diethyl phosphite anion, pinacolone enolate, and diphenylphosphide anion under irradiation to cleave one carbon-sulfur bond and form diethyl arylphosphonates, arylmethyl tert-butyl ketones, and aryldiphenylphosphines.Alkyl aryl sulfides and the related sulfones also experience carbon-sulfur bond cleavage under these conditions to produce arenethiols.Generally, these reactions occur in synthetically useful yields.The reactions of the anions with these sulfides, sulfoxides, and sulfones all require irradiation, but is notable that the reactions of diphenylphosphide anion occur in the visible region of the spectrum.Several lines of evidence suggest that the reaction proceeds via the familiar SRN1 pathway and that the photochemically-induced electron transfer occurs in an arene-anion complex.Thermochemical considerations dictate the cleavage direction in the anion radicals of unsymmetrical sulfides.
- Cheng, Carlos,Stock, Leon M.
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p. 2436 - 2443
(2007/10/02)
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- SOLVOLYSIS OF CHLORODIALKYL- AND DIARYLPHOSPHINES, DIALKYL PHOSPHOROCHLORIDITES AND DIALKYL PHOSPHINYL CHLORIDES
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The kinetics of solvolysis of chlorodiethylphosphine, chloro(di-n-propyl)phosphine and chlorodiphenylphosphine was studied by conductometry in pure ethanol and in various mixed solvents, and was compared with that of dialkyl phosphorochloridites and of dialkyl and diaryl phosphinyl chlorides.The rate of ethanolysis of chloro(di-n-propyl)phosphine was found to be larger at higher initial concentrations.Addition of sulfuric or perchloric acid enhanced the rate of solvolysis, while sodium perchlorate and lithium chloride had no influence.In ethanol containing water, the rate of solvolysis of chloro(di-n-propyl)phosphine is approximately proportional to the concentration of water.In formic acid, the solvolysis of chloro(di-n-propyl)phosphine is slower than in ethanol.Addition of acetone to ethanol increases the rate of solvolysis of chloro(di-n-propyl)phosphine - possibly due to a condensation reaction producing a 1-chloroalkyl dialkylphosphine oxide.The rate of ethanolysis of chloro(di-n-propyl)phosphine is considerably enhanced in the presence of isobutylamine, di-n-butylamine and triethylamine.The solvolysis of di-t-butylphosphinyl chloride in absolute ethanol is very much slower than that of dimethyl and diethyl phosphinyl chloride.Key words: Solvolysis; chlorodialkylphosphines; chlorodiphenylphosphine; dialkyl phosphorochloridite; dialkylphosphinyl chlorides; acid catalysis.
- Halmann, M.
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p. 251 - 262
(2007/10/02)
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- A Simple Synthesis and Some Synthetic Applications of Substituted Phosphide and Phosphinite Anions
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Based on data for the acidity relationship of phosphines and phosphinous acids and water in dimethyl sulfoxide and water, a simple method is reported for the generation of phosphide and phosphinite anions by the action of concentrated aqueous alkali on primary and secondary phosphines as well as phosphinous acids in dimethyl sulfoxide or other dipolar aprotic solvents.Alkylation of the anion yields secondary and tertiary phosphines, polyphosphines, functionally substituted phosphines as well as similarly substituted phosphine oxides.Phosphinous acids have beenalkylated in various solvents in two-phase systems containing concentrated aqueous alkali and tetrabutylammonium iodide as phase transfer catalyst.
- Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
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p. 198 - 208
(2007/10/02)
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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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- Diastereoselectivity in the Horner-Wittig Reaction: X-Ray Crystal Structure of 2-(1RS,2SR)-Diphenylphosphinoyl-1-phenylpropan-1-ol
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Ethyldiphenylphosphine oxide reacts with butyl-lithium and benzaldehyde to give the title compound which eliminates diphenylphosphinate ion in base to give Z-1-phenylpropene.The elimination is stereospecific and syn.The (1RS,2RS) isomer, prepared by sodium borohydride reduction of the corresponding ketone, gives E-1-phenylpropene.
- Buss, Anthony D.,Cruse, William B.,Kennard, Olga,Warren, Stuart
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p. 243 - 247
(2007/10/02)
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- Nucleophilic Substitution with Phosphide Anions Prepared by an Action of Sodium Dihydridobis(2-methoxyethanolato)aluminate on Phosphorus Compounds
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Phosphide anions, prepared by an action of sodium dihydridobis(2-methoxyethanolato)aluminate on derivatives of phosphine, phosphine oxide, or phosphorus esters, react with primary and secondary alkyl halides to produce phosphine derivatives having a newly formed phosphorus-carbon bond.The reactivity increases in the order of chloride N2 type process.
- Yamashita, Mitsuji,Suzuki, Nobuyoshi,Yamada, Manabu,Soeda, Yukio,Yamashita, Hiroaki,et al.
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p. 219 - 222
(2007/10/02)
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- SYNTHESE ET REDUCTION CHIMIQUE DE SELS DE VINYLENE-1,2 ET BUTADIENYLENE-1,4 BIPHOPHONIUMS
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1,2-vinylene- and 1,4-butadienylene-biphosphonium salts with labile groups on phosphorus (e.g. benzyl, 2-cyanoethyl, allyl or benzyl) are synthetized in the reaction of the corresponding tertiary phosphines with acetyl- or vinylacetyl bromide.When the salts are reacted with lithium aluminium hydride and with alkaline alcoholates or cyanides, the unsaturated bridge between the two phosphorus atoms is selectively cleaved to afford one or several tertiary phosphines.For each kind of cleavage a mechanism is proposed and discussed: with alcoholate or cyanide ions, the reaction gives rise to an ethynylphosphonium intermediate which accounts for the formation of the reaction products.
- Cristau, Henri-Jean,Labaudiniere, Lydie,Christol, Henri
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p. 359 - 372
(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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- PREPARATION OF DIPHENYLPHOSPHINE OXIDES BY DEOXYGENATION OF AN α-HYDROXYL GROUP WITH DIPHOSPHORUS TETRAIODIDE
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Deoxygenation of (1-hydroxyethyl)diphenylphosphine oxide derivatives was first achieved by a reaction with diphosphorus tetraiodide to give ethyldiphenylphosphine oxide derivatives.The reaction was also successful to prepare cyclohexyldiphenylphosphine oxide.
- Yamashita, Mitsuji,Tsunekawa, Kenji,Sugiura, Motoyuki,Oshikawa, Tatsuo,Inokawa, Saburo
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p. 1673 - 1674
(2007/10/02)
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