- Ylide-Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis
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Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross-coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron-rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide-functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.
- Scherpf, Thorsten,Schwarz, Christopher,Scharf, Lennart T.,Zur, Jana-Alina,Helbig, Andreas,Gessner, Viktoria H.
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supporting information
p. 12859 - 12864
(2018/09/25)
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- METHOD FOR PREPARING HALOGENATED ORGANOPHOSPHINES
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The present application relates to a process for preparing a halogenated organophosphine, comprising reacting a primary or secondary organophosphine with a halogenating agent selected from (A) a compound of formula (I) : (HaI)3C-C(O)-X (I) wherein X is selected from alkyl, aryl, aralkyl, alkaryl, cycloalkyl, NR1R2, C(HaI)3, OR3, -0-C(O)-R3', or -Y-Z-Y-C(O)- C(HaI)3; R1 and R2 are each independently selected from hydrogen, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl; R3 is selected from H, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, or triorganosilyl; R3' is selected from C(HaI)3, alkyl, aryl, aralkyl, alkaryl, cycloalkyl; Y is independently selected from 0 or NH; Z is independently selected from alkylene, arylene, aralkylene, alkarylene, or cycloakylene; and Hal is selected from Cl or Br; or (B) a derivative of a polyol, polyamine or polyaminoalcohol comprising two or more hydroxyl and/or amino groups, in which a hydrogen atom in each of the hydroxyl and/or amino groups is replaced with a group -C(O)-C(HaI)3, wherein Hal is selected from Cl or Br.
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Page/Page column 19
(2009/12/28)
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- Synthesis, structure, magnetism and nuclease activity of tetranuclear copper(ii) phosphonates containing ancillary 2,2′-bipyridine or 1,10-phenanthroline ligands
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The reaction of cyclohexylphosphonic acid (C6H 11PO3H2), anhydrous CuCl2 and 2,2′-bipyridine (bpy) in the presence of triethylamine followed by a metathesis reaction with KNO3 afforded [Cu
- Chandrasekhar, Vadapalli,Azhakar, Ramachandran,Senapati, Tapas,Thilagar, Pakkirisamy,Ghosh, Surajit,Verma, Sandeep,Boomishankar, Ramamoorthy,Steiner, Alexander,Koegerler, Paul
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p. 1150 - 1160
(2008/09/18)
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- [2+1] Cycloadditions of terminal alkynes to norbornene derivatives catalyzed by palladium complexes with phosphinous acid ligands
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(Chemical Equation Presented) Two plus one makes three-membered rings in an unusual [2+1] cycloaddition of phenylethyne with norbornadiene as catalyzed by a new palladium(II) complex with phosphinous acid ligands (see scheme). A related complex (cyclohexy
- Bigeault, Julie,Giordano, Laurent,Buono, Gerard
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p. 4753 - 4757
(2007/10/03)
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- Synthesis and properties of new fused bicyclic compounds containing P-B- S linkages
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New bicyclic compounds, (P-B)-12-phenyl-12H-dibenzo[d,g]-[ 1,3,6,2]dithiaphosphaborocine (3a) and (P-B)-12-cyclohexyl-12H-dibenzo [d,g][1,3,6,2]dithiaphosphaborocine (3b), were synthesized by the reaction of phenyl- and cyclohexylbis(2-mercaptophenyl)phos
- Hirakawa, Eiji,Takeda, Nobuhiro,Imamoto, Tsuneo
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p. 667 - 679
(2007/10/03)
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- Process for making chlorophosphines and thiophosphinic acid chlorides, and 9-chloro-9-thioxo-9-phosphabicyclononanes
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Chlorophosphines or thiophosphinic acid chlorides of the general formulae RPCl2, R2 PCl or R2 P(=S)Cl are made from feed materials selected from hydrogen-functional primary or secondary phosphines or secondary phosphine sulfides, where R stands for identical or different, linear or branched, substituted or unsubstituted alkyl radicals having from 1-16 carbon atoms, aryl radicals, aralkyl radicals or alkylaryl radicals having from 6-9 carbon atoms or cycloalkyl radicals having from 5-10 carbon atoms. To this end, the feed materials are reacted with phosphorus pentachloride, or with chlorine gas in the presence of phosphorus trichloride at temperatures within the range -78° to +145° C. It is possible for two radicals R to be linked together by one or two substituted or unsubstituted hydrocarbon chains having from 1-4 carbon atoms.
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- Process for making chlorophosphanes, phosphinic acid chlorides or thiophosphinic acid chloride, and novel isomeric mixture consisting of chloro-phosphabicyclononanes
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The disclosure relates to a process for making chlorophosphanes from primary or secondary phosphanes, or phosphinic acid chlorides or thiophosphinic acid chlorides from secondary phosphane oxides or sulfides, wherein the respective starting materials are reacted with hexachloroethane at temperatures of 20° to 180° C. The disclosure also provides as a novel chemical substance an isomeric mixture consisting of 9-Cl-9-phosphabicyclononane [3.3.1] and 9-Cl-9-phosphabicyclononane [4.2.1].
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- ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN, XXI. Darstellung von Organobromphosphanen aus RPCl2 und R2PCl durch Halogenaustausch.
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Several methods for the preparation of organobromophosphanes from RPCl2 and R2PCl by halogen exchange are described.In case of aryl compounds optimal results are obtained by equilibration of the chlorophosphanes with PBr3 followed by distillation or cryst
- Hinke, Axel,Kuchen, Wilhelm
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