- Method for simultaneously synthesizing phosphine chiral center second-level/third-level phosphine oxide compound under catalysis of palladium/chiral ligand
-
The invention discloses a method for simultaneously synthesizing phosphine chiral center second-level/third-level phosphine oxide compounds under catalysis of palladium/chiral ligands. The method comprises the following steps: in the presence of an organic solvent and an additive, carrying out kinetic resolution reaction on racemic secondary phosphine oxide as shown in a formula I and an alkylating reagent as shown in a formula II under the catalysis of a palladium catalyst/chiral ligand Xiao-Phos to obtain phosphine chiral center secondary phosphine oxide as shown in a formula III and a phosphine chiral center tertiary phosphine oxide compound as shown in a formula IV, wherein a reaction formula is shown as a formula (a). The raw materials are stable and easy to obtain, the method is simple, and the substrate application range is wide. According to the invention, an efficient route with atom economy is provided for kinetic resolution of racemic secondary phosphine oxide and preparation of a phosphine chiral center compound, the follow-up synthesis application of the two products with high optical activity is expanded, and the synthetic method provided by the invention has very high practical application value.
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Paragraph 0040-0044; 0092-0096
(2022/01/10)
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- Enantioseparation of P-Stereogenic Secondary Phosphine Oxides and Their Stereospecific Transformation to Various Tertiary Phosphine Oxides and a Thiophosphinate
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Secondary phosphine oxides incorporating various aryl and alkyl groups were synthesized in racemic form, and these products formed the library reported in this study. TADDOL derivatives were used to obtain the optical resolution of these P-stereogenic sec
- Bagi, Péter,Fogassy, Elemér,Herbay, Réka,Holczbauer, Tamás,Keglevich, Gy?rgy,Nagy, Petra,Szemesi, Péter,Varga, Bence
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p. 14493 - 14507
(2021/10/25)
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- Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation
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P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-se
- Dai, Qiang,Liu, Lu,Zhang, Junliang
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p. 27247 - 27252
(2021/11/17)
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- Desymmetrization of Phosphinic Acids via Pd-Catalyzed Asymmetric Allylic Alkylation: Rapid Access to P-Chiral Phosphinates
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The synthesis of P-chiral compounds is challenging, especially since useful catalytic methods for preparing such molecules are scarce. Herein we disclose a desymmetrization that employs phosphinic acids as prochiral nucleophiles in a Pd-catalyzed asymmetr
- Trost, Barry M.,Spohr, Simon M.,Rolka, Alessa B.,Kalnmals, Christopher A.
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p. 14098 - 14103
(2019/10/11)
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- General and Stereoselective Method for the Synthesis of Sterically Congested and Structurally Diverse P-Stereogenic Secondary Phosphine Oxides
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A general and efficient method for the synthesis of bulky and structurally diverse P-stereogenic chiral secondary phosphine oxides (SPOs) by using readily available chiral amino alcohol templates is described. These chiral SPOs could be used as chiral building blocks for the synthesis of difficult-to-access bulky P-stereogenic phosphine compounds or ligands for organic catalysis.
- Han, Zhengxu S.,Wu, Hao,Xu, Yibo,Zhang, Yongda,Qu, Bo,Li, Zhibin,Caldwell, Donald R.,Fandrick, Keith R.,Zhang, Li,Roschangar, Frank,Song, Jinhua J.,Senanayake, Chris H.
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supporting information
p. 1796 - 1799
(2017/04/11)
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- Iridium versus Iridium: Nanocluster and Monometallic Catalysts Carrying the Same Ligand Behave Differently
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A specific secondary phosphine oxide (SPO) ligand (tert-butyl(phenyl)phosphine oxide) was employed to generate two iridium catalysts, an Ir–SPO complex and IrNPs (iridium nanoparticles) ligated with SPO ligands, which were compared mutually and with several supported iridium catalysts with the aim to establish the differences in their catalytic properties. The Ir–SPO-based catalysts showed totally different activities and selectivities in the hydrogenation of various substituted aldehydes, in which H2is likely cleaved by a metal–ligand cooperation, that is, the SPO ligand and a neighboring metal centre operate in tandem to activate the hydrogen molecule. In addition, the supported IrNPs behave very differently from both Ir–SPO catalysts. This study exemplifies perfectly the advantages and disadvantages related to the use of the main types of catalysts, and thus the dissimilarities between them.
- Cano, Israel,Martínez-Prieto, Luis M.,Chaudret, Bruno,van Leeuwen, Piet W. N. M.
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p. 1444 - 1450
(2017/02/05)
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- Synthesis of P-stereogenic secondary phosphine oxides using α-d-glucosamine as a chiral precursor
-
Secondary phosphine oxides were synthesized using a two-step procedure: a basic hydrolysis of oxazaphospholidine SP-2 to form the secondary phosphinate RP-4, followed by the stereoselective nucleophilic attack of organometallic reagents to obtain the expected enantioenriched secondary phosphine oxides.
- Copey, Laurent,Jean-Gérard, Ludivine,Andrioletti, Bruno,Framery, Eric
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p. 543 - 545
(2016/01/20)
-
- Enantioselective Cu-Catalyzed Arylation of Secondary Phosphine Oxides with Diaryliodonium Salts toward the Synthesis of P-Chiral Phosphines
-
Catalytic synthesis of nonracemic P-chiral phosphine derivatives remains a significant challenge. Here we report Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts for the synthesis of tertiary phosphine oxides
- Beaud, Rodolphe,Phipps, Robert J.,Gaunt, Matthew J.
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p. 13183 - 13186
(2016/10/22)
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- H-adamantylphosphinates as universal precursors of P-stereogenic compounds
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A new family of H-adamantylphosphinates as universal precursors of P-stereogenic ligands was obtained in one step from commercial chlorophosphines. Both enantiomers of these air- and moisture-stable intermediates can easily be separated by semipreparative chiral HPLC on a gram scale and individually undergo stereoselective transformations to afford each enantiomer of a set of P-stereogenic compounds such as secondary phosphine oxides and boron-protected monophosphines.
- Gatineau, David,Nguyen, Duc Hanh,Hérault, Damien,Vanthuyne, Nicolas,Leclaire, Julien,Giordano, Laurent,Buono, Gérard
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p. 4132 - 4141
(2015/05/05)
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- P-STEREOGENIC CHIRAL PRECURSOR OF CHIRAL LIGANDS AND USE THEREOF
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The present invention concerns phosphinate universal P-stereogenic chiral precursors of formula (I) for chiral ligands, preparation processes thereof and their use for the preparation of optically pure or enriched chiral ligands. Claimed are formula (I) c
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-
- Consecutive dynamic resolutions of phosphine oxides
-
A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides.
- Kortmann, Felix A.,Chang, Mu-Chieh,Otten, Edwin,Couzijn, Erik P. A.,Lutz, Martin,Minnaard, Adriaan J.
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p. 1322 - 1327
(2014/03/21)
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- Copper(I)-induced sulfenylation of H-phosphonates, H-phosphonites and phosphine oxides with aryl/alkylsulfonylhydrazides as a thiol surrogate
-
Aerobic dehydrogenative sulfenylation of H-phosphonites, and phosphine oxides with aryl/alkylsulfonyl hydrazides catalyzed by a sub-stoichiometric amount of copper iodide has been accomplished. This protocol is compatible with functional groups, and results in various thiophosphate derivatives in good to high yields.
- Kumaraswamy, Gullapalli,Raju, Ragam
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supporting information
p. 2591 - 2598
(2014/09/29)
-
- Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride
-
A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.
- Rajendran, Kamalraj V.,Gilheany, Declan G.
-
supporting information; scheme or table
p. 817 - 819
(2012/02/03)
-
- Bulky, optically active P-stereogenic phosphine-boranes from pure H-menthylphosphinates
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The transformation of readily available pure-H-menthylphosphinates into chiral phosphinous acid-boranes permits the elaboration of bulky P-stereogenic secondary phosphine-boranes. Taking advantage of the synthetic potential of these compounds, a broad range of hindered P-chiral tertiary phosphine-boranes has been prepared with excellent enantiomeric excesses. The utility of bulky o-tolylphosphines was illustrated by the synthesis of a rare enantiopure phosphapalladacycle (SP,SP)-12.
- Gatineau, David,Giordano, Laurent,Buono, Gerard
-
supporting information; experimental part
p. 10728 - 10731
(2011/09/14)
-
- Stereoselective addition of grignard reagents to new P-chirogenic N-phosphinoylbenzaldimines: Effect of the phosphorus substituents on the stereoselectivity
-
Several phosphinoylimines have been synthesized in five steps by starting from the appropriate phosphane oxide and were then treated with methylmagnesium bromide to give both diastereoisomers in high yields and with promising diastereomeric ratios. Then N-[(tert-butyl)(phenyl)phosphinoyl]benzaldimine, which displayed the best results, was subjected to the 1,2-addition of various Grignard reagents to evaluate the best chiral induction due to the stereogenic phosphorus atom. The corresponding adducts were obtained in excellent yields and with moderate to excellent diastereoisomeric ratios. Copyright
- Notar Francesco, Irene,Egloff, Coraline,Wagner, Alain,Colobert, Francoise
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p. 4037 - 4045
(2011/09/15)
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- Stereoselective addition of Grignard reagents to new P-chirogenic N-phosphinoylimines
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The addition of various Grignard reagents to P-t-butyl-P-phenyl-N- phosphinoyl benzaldimine provides a stereoselective method for the synthesis of chiral phosphinoylamines. The Royal Society of Chemistry.
- Francesco, Irene Notar,Wagner, Alain,Colobert, Francoise
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scheme or table
p. 2139 - 2141
(2010/07/04)
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- Steric control in the synthesis of phosphinous acid-coordinated mono- and binuclear platinum(II) complexes
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Several phosphinous acid-coordinated platinum complexes were prepared and characterized. In the presence of secondary phosphine oxide (2 equiv), PtCl 2(cod) was converted to a series of cis/trans platinum complexes PtCl2[R1R2POH]2 featuring phosphinous acids (PAs) as ligands (20-29). A balance between the steric and electronic effects of ligands governs their coordination mode. NMR experiments and density functional theory calculations show that the anti conformer for trans complexes is favored by intramolecular HCl bonding. PtCl 2[R1R2POH]2 treated with NEt 3 (1 equiv) gave bimetallic platinum complexes cis-[Pt 2(μ-Cl)2{(R1R2PO) 2H}2] characterized by 31P NMR and X-ray diffraction. An unusual monometallic platinum complex, cis-[PtCl 2{(i-Bu)2PO}2H]-[HNEt 3]+ (30), was isolated and characterized as a possible intermediate in the formation of dinuclear species. Silver acetate and triethylamine both reacted with PtCl2[(t-Bu)2POH] 2 to yield new bulky Pt(κ2-acetato){[(t-Bu) 2PO]2H} platinum complex 31. The structure of complexes 20d (R1 = Ph, R2 = Cy), 21 (R1 = Ph, R 2 = t-Bu), 21d (R1 = Ph, R2 = t-Bu), 24 (R 1 = R2 = t-Bu), 25 (R1 = R2 = Cy), 30 (R1 = R2 = i-Bu), and 31 (R1 = R2 = t-Bu) were determined by X-ray diffraction.
- Achard, Thierry,Giordano, Laurent,Tenaglia, Alphonse,Gimbert, Yves,Buono, Gerard
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scheme or table
p. 3936 - 3950
(2010/12/25)
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- On the resolution of secondary phosphine oxides via diastereomeric complex formation: The case of tert-butylphenylphosphine oxide
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The secondary phosphine oxide, t-BuPhHP=O, the most prominent chiral member of this compound class, has been resolved in high yield and with excellent ee. This resolution discloses an efficient route to enantiopure phosphorus compounds. Georg Thieme Verla
- Holt, Jarle,Maj, Anna M.,Schudde, Ebe P.,Pietrusiewicz, K. Michal,Sieron, Lelsaw,Wieczorek, Wanda,Jerphagnon, Thomas,Arends, Isabel W. C. E.,Hanefeld, Ulf,Minnaard, Adriaan J.
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experimental part
p. 2061 - 2065
(2010/01/16)
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- New look into the synthesis of polyhalogenoarylphosphanes
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The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y- (1a-c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O-(1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a-c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X 5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(Bu t)P-X. Taylor & Francis Group, LLC.
- Nycz, Jacek E.
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experimental part
p. 2605 - 2612
(2010/08/06)
-
- Enantiopure tert-butyl(phenyl)phosphine oxide. Chirality-recognition ability and mechanism
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When enantiopure tert-butyl(phenyl)phosphine oxide 1 was used as a resolving agent, it showed an acceptable to good chirality-recognition ability for several kinds of racemic carboxylic acids 2. A study on a chirality-recognition mechanism based on X-ray crystallographic analyses of the diastereomeric complexes of 2 with 1 revealed that the complex crystals consisted of helical columns and that 1 was not responsible for the formation of the helical column and occupied a void between the columns; although 1 interacted with 2 via a hydrogen bond to primarily form a pair with 2, the complex crystals were mainly stabilized by the accumulation of weak interactions, such as CH/π, π/π and CH...O interactions, between 1/1, 1/2 and 2/2.
- Ribeiro, Nigel,Saigo, Kazuhiko
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scheme or table
p. 2704 - 2708
(2010/04/29)
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- Stereospecific nucleophilic substitution of optically pure H-phosphinates: A general way for the preparation of chiral P-stereogenic phosphine oxides
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Contrary to the generally held view, it is found that the rapid epimerization of (-)-menthyl (RP)-phenylphosphinate under basic conditions is not due to the so far believed inherent stereolability of its corresponding anion but due to a reactio
- Xu, Qing,Zhao, Chang-Qiu,Han, Li-Biao
-
supporting information; experimental part
p. 12648 - 12655
(2009/05/09)
-
- Resolution and stereochemistry of tert-butylphenylphosphinous acid-borane
-
(Chemical Equation Presented) A combined use of ephedrine and cinchonine as resolving agents enabled facile resolution of racemic tert- butylphenylphosphinous acid-borane (1) into the two enantiomers in ca. 31-32% yield each. The resolved 1 served as a mo
- Stankevic, Marek,Pietrusiewicz, K. Michal
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p. 816 - 822
(2007/10/03)
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- Enantioselective synthesis of secondary phosphine oxides from (RP)-(-)-menthyl hydrogenophenylphosphinate
-
Alkyl- and arylphenylphosphine oxides can easily be synthesized with an excellent enantiomeric excess starting from diastereomerically pure (RP)-(-)-menthylhydrogenophenylphosphinate and organometallic reagents.
- Leyris, Adeline,Bigeault, Julie,Nuel, Didier,Giordano, Laurent,Buono, Gérard
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p. 5247 - 5250
(2008/02/08)
-
- Aminophosphine oxides in a pyridine series. Studies on the cleavage of pyridine-2- and pyridine-4-yl-(N-benzylamino)-methyldiphenylphosphine oxides in acidic solutions
-
The synthesis and reactions of 1-(N-benzylamino)-1-(2-pyridyl)- and 1-(N-benzylamino)-1-(4-pyridyl)-methyldiphenylphosphine oxides are described. It was found that these compounds were exceptionally easy to cleave in aqueous sulfuric acid solutions to form diphenylphosphinic acid and the corresponding N-(pyridylmethyl)-benzylamines. The structure of a single diastereoisomer, that is, the (R)-(+)-1-[N-(α-methylbenzylamino)]-1-(4-pyridyl)-(S)-methyldiphen ylphosphine oxide was determined by X-ray crystallography. The acidic alcoholysis of the selected model chiral pyridine aminophosphine oxides was investigated by means of 31P NMR spectroscopy. The cleavage kinetics were also studied. On the basis of the obtained results, a mechanism of the cleavage was formulated.
- Goldeman, Waldemar,Olszewski, Tomasz K.,Boduszek, Bogdan,Sawka-Dobrowolska, Wanda
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p. 4506 - 4518
(2007/10/03)
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- Enantioselective synthesis of both enantiomers of tert-butylphenylphosphine oxide from (S)-prolinol
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Both enantiomers of tert-butylphenylphosphine oxide can be easily synthesised starting from (S)-prolinol-based oxazaphospholidine.
- Leyris, Adeline,Nuel, Didier,Giordano, Laurent,Achard, Mathieu,Buono, Gérard
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p. 8677 - 8680
(2007/10/03)
-
- A superior method for the reduction of secondary phosphine oxides
-
(Chemical Equation Presented) Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70°C. This new reduction has distinct advantages over existing technologies.
- Busacca, Carl A.,Lorenz, Jon C.,Grinberg, Nelu,Haddad, Nizar,Hrapchak, Matt,Latli, Bachir,Lee, Heewon,Sabila, Paul,Saha, Anjan,Sarvestani, Max,Shen, Sherry,Varsolona, Richard,Wei, Xudong,Senanayake, Chris H.
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p. 4277 - 4280
(2007/10/03)
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- The synthesis and reactivity of phosphinous acid-boranes
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Phosphinic acid chlorides are converted directly into phosphinous acid-boranes in a process utilizing BH3-THF complex as a reducing agent. The process is general and affords phosphinous acid-boranes in good to very high yields. Phosphinous acid
- Stankevic, Marek,Pietrusiewicz, K. Michal
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p. 1279 - 1290
(2007/10/03)
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- Stereoselective reactions of optically active derivatives of α-methylbenzylaminophosphine
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A number of N-(α-methylbenzyl) phosphorus amides were synthesized, and their stereochemical properties were studied. Reactions of achiral chlorophosphines with optically active α-methylbenzylamine are accompanied by asymmetric induction at the phosphorus
- Kolodyazhnyi,Andrushko,Grishkun
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p. 515 - 522
(2007/10/03)
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- Aminohydroxy phosphine oxide ligands in ruthenium-catalysed asymmetric transfer hydrogenation reactions
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A class of aminohydroxy phosphine oxide ligands was derived from optically active amino alcohols, containing stereogenic centres at phosphorus and at carbon. Their activities and selectivities in the asymmetric transfer hydrogenation reaction were assesse
- Cheng, Xiaohui,Horton, Peter N.,Hursthouse, Michael B.,Hii, King Kuok
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p. 2241 - 2246
(2007/10/03)
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- Asymmetric synthesis of chiral N-(1-methylbenzyl)aminophosphines
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The reactions of chlorophosphines 1 with (S)- or (R)-1-methylbenzylamines 2 proceed stereoselectively to give N-(1-methylbenzyl)aminophosphines 3, which were isolated as crystalline borane complexes with 100% diastereomeric purity. The absolute configuration of the new chiral compounds was established by X-ray analysis and chemical extrapolation.
- Kolodiazhnyi, Oleg I.,Gryshkun, Evgenyi V.,Andrushko, Natalia V.,Freytag, Matthias,Jones, Peter G.,Schmutzler, Reinhard
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p. 181 - 183
(2007/10/03)
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- Reaction of metallated tert-butyl(phenyl)phosphane oxide with electrophiles as a route to functionalized tertiary phosphane oxides: Alkylation reactions
-
P-Chiral tertiary phosphane oxides have been prepared from each of the secondary phosphane oxides racemic 1, (S(p))-(-)-4 and (Rp)-(+)-tert-butylphenylphosphane oxide (5) by lithiation with LDA or nBuLi, or sodiation with sodium hydride, in THF, and then by treatment with a series of primary alkyl halides. Doubly P-chiral ditertiary bis(phosphane oxides) are also obtained from these metallated secondary phosphane oxides by treatment with electrophiles based on straight-chain, tartrate-derived, and bishalomethylarene dihalides. In general, the bis-phosphane oxides are obtained in good yields. However, when the α,ω-dihalide bears an embedded heteroatom (O or Si), yields are diminished. The enantiomeric purity of each of the products was assessed through admixture with (R(p))- and (S(p))-tert-butyl(phenyl)phosphanylthioic acids and measurement of the tert-butyl resonances in the 1H-NMR spectra. In all cases, the act of metallation of the enantiomerically pure secondary phosphane oxide followed by its alkylation is not accompanied by detectable racemization. This method for preparing P-chiral tertiary phosphane oxides is therefore more straightforward than those described previously.
- Haynes, Richard K.,Au-Yeung, Tin-Lok,Chan, Wai-Kuen,Lam, Wai-Lun,Li, Zhi-Yi,Yeung, Lam-Lung,Chan, Albert S. C.,Li, Pauline,Koen, Mark,Mitchell, Craig R.,Vonwiller, Simone C.
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p. 3205 - 3216
(2007/10/03)
-
- Reductive cleavage of the halogen-phosphorus, oxygen-phosphorus and phosphorus-phosphorus bonds with alkali metals
-
The reduction of phosphorus acid chlorides as well as hypophosphates, pyrophosphates and mixed P(III)-P(V) anhydrides with alkali metals (Li, Na, K) in NH3 liq. / THF solution and potassium naphthalenide was investigated. It was found that this type of phosphorus compounds easily undergo reduction: a) >P(O)Cl to >P(O)H; b) >P(O)P(O)P(O)H; c) >P(O)-O-P(O)P(O)OH and >P(O)H; d) >P(O)-O-PP(O)O- and >P-. The results of our experiments strongly suggest that the mixed P(III)-P(V) anhydride is reduced by potassium naphthalenide in THF with the cleavage of the P(III)-oxygen bond.
- Nycz, Jacek,Rachon, Janusz
-
-
- New procedures for the resolution of chiral tert-butylphenylphosphine oxide and some of its reactions
-
Racemic t-butylphenylphosphine oxide was resolved via formation of diastereoisomeric complexes with (+)-(R)-1,1'-binaphthalene-2,2'-diol and (+)-(S)-mandelic acid. With the latter complexing agent, separation of the essentially enantiopure (-)-(S)-enantio
- Drabowicz, Joezef,Lyzwa, Piotr,Omelanczuk, Jan,Pietrusiewicz, K. Michal,Mikolajczyk, Marian
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p. 2757 - 2763
(2007/10/03)
-
- Preparation of Enantiomerically Pure Tertiary Phosphine Oxides from, and Assay of Enantiomeric Purity with, (Rp)- and (Sp)-tert-Butylphenylphosphinothioic Acids
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A convenient multigram scale method has been developed for preparation of enantiomerically-pure (Rp)- and (Sp)-tertiary phosphine oxides including allyl- and but-2-enyl-tert-butylphenylphosphine oxides wherein (Rp)- and (S
- Haynes, Richard K.,Freeman, Richard N.,Mitchell, Craig R.,Vonwiller, Simone C.
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p. 2919 - 2921
(2007/10/02)
-
- Unexpected Opposite Stereochemistries and Different Mechanisms of Nucleophilic Substitution Reactions of Homochiral tert-Butylphenylthiophosphinoyl Chloride and Bromide
-
Reactions of ethylmercapto (ethylsulfanyl) anion with homochiral (+)-(S)-tert-butylphenylphosphinochloridothionate 2 and (-)-(S)-tert-butylphenylphosphinobromidothionate 3 proceed with inversion and retention at phosphorus, respectively, as a consequence
- Omelanczuk, Jan,Mikolajczyk, Marian
-
p. 2223 - 2224
(2007/10/02)
-
- TRANSFORMATION OF ORGANOPHOSPHORUS S-TRIFLUOROMETHYLTHIOATES RR'P(O)SCF3 INTO FLUORIDES RR'P(O)F. STEREOCHEMICAL ASPECTS OF THIOCARBONYL FLUORIDE EXTRUSION
-
The stereochemical course of the thermal or by nucleophiles catalyzed extrusion reaction of thiocarbonyl fluoride from two diastereomeric (6) and optically active (10) organophosphorus S-trifluoromethylthioates has been investigated.To explain the observed retention of configuration at phosphorus in fluoridates 7 formed in the thermal reactions, a four center transition state for such reactions has been proposed.The lack of the stereoselectivity in the catalyzed reactions of 6, and the observed racemization of the final product 11 are briefly discussed.
- Lopusinski, Andrezej
-
p. 383 - 390
(2007/10/02)
-
- OPTICALLY ACTIVE TRIORGANOSILYL ESTERS OF PHOSPHORUS. SYNTHESIS AND STRUCTURE
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We report this synthesis of the first optically active silyl esters of phosphorus having two centres of chirality : one on silicon and the other on phosphorus.Compounds are obtained of general formula : t-BuPhP(X)YSiαNpPhMe X,Y=O, O(1); S, O(2); Se, O(3); S, S(4); doublet, O(5) including 1 and 3 with optical activity located on Si, 2 and 5 with the activity on Si or P and on both these centres, 4 only racemic.Absolute configurations are determined. 31P and 29Si NMR spectra of these models and their trimethylsilyl analogues are reported.The triorganosilyl group is always preferentially bound to phosphorus through oxygen atom.Surprisingly, diastereotopic NMR chemical shifts exclude the fast 1,3 migration in esters 1 and 4. 29Si NMR spectra correspond to a tetracoordinate silicon atom.
- Chojnowski, J.,Cypryk, M.,Michalski, J.,Wozniak, L.,Corriu, R.,Lanneau, G.
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p. 385 - 398
(2007/10/02)
-
- Phosphino Sulphonates, a Type of PIII-anhydride and Their Isomerisation into Phosphinoyl Sulphinates: a Novel Rearrangement in Phosphorus-Sulphur Chemistry
-
The imidazolides (1) react smoothly with RSO3H to afford a novel class of trico-ordinate phosphorus anhydride, the phosphino sulphonates (2); under suitable structural circumstances the compounds (2) undergo a novel type of rearrangement, (2) -> (6), which provides the first example of a phosphinoyl sulphinate structure (6).
- Dabkowski, Wojciech,Michalski, Jan,Skrzypczynski, Zbigniew
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p. 1260 - 1261
(2007/10/02)
-
- THIOCYANATION OF DIALKYL PHOSPHITES AND THEIR STRUCTURAL ANALOGUES BY THIOCYANOGEN (SCN)2: MECHANISM AND STEREOCHEMISTRY
-
The thiocyanation of organophosphorus compounds containing >P(X)H functional groups (X=O,S) has been reinvestigated.The reaction was shown to be highly stereospecific and proceeds with the retention of configuration at P via the thiocyanidate >P(O)SCN structure.The thiocyanidates rearrange into the isothiocyanidates >P(O)NCS with a rate depending on structure of substrates and reaction conditions.The thiocyanation reaction of dialkyl phosphite and their structural analogues offers an excellent route to the isothiocyanidates >P(X)NCS and in some cases also the thiocyanidates >P(X)SCN.
- Lopusinski, A.,Luczak, L.,Michalski, J.
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p. 679 - 683
(2007/10/02)
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- STEREOCHEMISTRY OF THE ACYCLIC PHOSPHONO- AND PHOSPHINO-THIOCYANIDE ISOMERISATION INTO CORRESPONDING ISOTHIOCYANIDATES SYNTHESIS OF OPTICALLY ACTIVE THIOCYANIDATES >P(O)SCN ISOTHIOCYANIDATES >P(O)NCS, ISOCYANIDATES >P(O)NCO AND RELATED PHOSPHORYLATED DERI
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Optically active t-butylphenylphosphinothiocyanidate ButPhP(O)SCN 3 and t-butyl-O-methyl-phosphonothiocyanidate But(MeO)P(O)SCN 7 have been prepared by condensation of the corresponding sulphenyl chlorides >P(O)SCl with trimethylsily
- Kopusinski, A.,Kuczak, L.,Michalski, J.,Kabachnik, M. M.,Moriyama, M.
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p. 2011 - 2020
(2007/10/02)
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- Investigations on Steric and Electronic Influences on the Reactivity of Acetyl(diorganyl)phosphanes and their Oxides
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The aliphatic-aromatic and pure aromatic acetyl(diorganyl)phosphanes CH3C(O)PR1R2 (1a-e) , of which only 1e is stable towards molecular oxygen, can be obtained from CH3C(O)Cl and (CH3)3SiPR1R2 or HPR1R2 in the presence of NEt3 .The corresponding oxides CH3C(O)P(O)R1R2 (2a-e) are formed by reaction of 2O with HP(O)R1R2 .With the lastnamed oxides however only 2a, b, d react to the stable alcohols CH3C2OH (3a, b, d).The reactivity of the newly prepared compounds 1a-e, 2a-e and 3a, b, d depends on electronic and steric influences of the organic residues linked to the phosphorus.
- Lindner, Ekkehard,Frey, Gerhard
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p. 3268 - 3274
(2007/10/02)
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