Enantioselective synthesis of α‐phosphanyl ketones and 2‐phosphanyl alcohols

An efficient, highly enantioselective methodology for the synthesis of α-phosphanyl ketones 7 and 2-phosphanyl alcohols 12 and 13, important hemilable ligands for enantioselective homogeneous catalysis and chiral building blocks in general, has been developed. The key step of this first enantio-selective synthesis of α-phosphanyl ketones is the diastereo-selective phosphanylation of SAMP hydrazones 2 to produce α-phosphanyl hydrazones, isolated as the more stable borane adducts 6. Subsequent ozonolysis afforded α-phosphanyl ketones 7. The enantioselective synthesis of 2-phosphanyl alcohols 12 and 13 has been accomplished by two fundamentally different procedures: the phosphanylation of unsubstituted chiral aldehyde hydrazones 9 and the alkylation of α-diphenylphopshanyl acetaldehyde SAMP hydrazone 10. After separation of the minor diastereomer, the borane-protected α-phosphanyl aldehyde hydrazones 11 were converted to unprotected 2-phosphanyl alcohols 13 by ozonolysis, reduction and removal of the borane group. The absolute configuration of the functionalized phosphanes was determined by X-ray analysis, NOE experiments or polarimetry.

[1]  D. Enders,et al.  Enantioselective Synthesis of 2-Phosphino Alcohols via Phosphinylation of Metalated Chiral Aldehyde Hydrazones , 1996 .

[2]  D. Enders,et al.  Enantioselektive Synthese von α‐Phosphinoketonen. Vorläufige Mitteilung , 1996 .

[3]  H. Werner,et al.  Synthesis of Tridentate Phosphine Ligands RP((CH2)nY)2 (Y: OR′ or CO2R′ , n = 1 or 2) and Some Bidentate Chiral Phosphines R2PCH(CH3)CO2Me. , 1996 .

[4]  B. Fell,et al.  Zweiphasen-Hydroformylierung höhermolekularer Olefine mit ethoxyliertem Tris-(p-hydroxyphenyl)phosphan als Komplexligand für den Rhodiumcarbonyl-Katalysator , 1996 .

[5]  A. Börner,et al.  Hydroxyalkylphosphines in asymmetric hydrogenations , 1995 .

[6]  A. Börner,et al.  β-Alkoxy- and β-Hydroxyalkylphosphanes as Ligands in the Stereoselective Hydrogenation — A Comparison , 1995 .

[7]  G. Muller,et al.  Synthesis of monohydroxy -methyl- and -ethyl-phosphines PPh2CHROH , 1995 .

[8]  S. Coles,et al.  Synthesis and characterization of group 10 metal complexes with a new trifunctional ether phosphine. The X-ray crystal structures of bis[bis(2-ethoxyethyl)benzylphosphine] dichloronickel(II) and bis[bis(2-ethoxyethyl)benzylphosphine]chlorophenylnickel(II) , 1995 .

[9]  T. Livinghouse,et al.  AN EFFICIENT PROCEDURE FOR THE SYNTHESIS OF ELECTRON RICH BISPHOSPHINES CONTAINING HOMOCHIRAL BACKBONES , 1994 .

[10]  A. Börner,et al.  Synthesis of an optically active hydroxy diphosphine, a new ligand for asymmetric catalysis , 1994 .

[11]  T. Mitchell,et al.  Approaches to water-soluble phosphines: II. Free radical addition reactions of phenylphosphines , 1994 .

[12]  K. Yanagi,et al.  Catalytic Asymmetric Reduction of Allylic Esters with Formic Acid Catalyzed by Palladium-MOP Complexes , 1994 .

[13]  W. Ruth,et al.  Synthesis and catalytic properties of an acyclic analogue of hydroxy norphos , 1994 .

[14]  T. Livinghouse,et al.  On the asymmetric rh(I) catalyzed [4+2] cycloisomerization reaction. Electronic and torsional ligand control of absolute stereoselection. , 1994 .

[15]  J. Ward,et al.  Concise synthesis of enantiomerically pure cis- and trans-3-(diphenylphosphino)-4-hydroxytetrahydrofurans , 1993 .

[16]  K. Achiwa,et al.  Synthesis and application of chiral bisphosphine ligands containing a hetero-functional group , 1993 .

[17]  H. Brisset,et al.  Phosphine-borane complexes; direct use in asymmetric catalysis , 1993 .

[18]  U. Nagel,et al.  Catalytic Hydrogenation with Rhodium Complexes Containing dipamp‐pyrphos Hybrid Ligands , 1993 .

[19]  K. Nozaki,et al.  Highly enantioselective hydroformylation of olefins catalyzed by new phosphine phosphite-rhodium(I) complexes , 1993 .

[20]  U. Nagel,et al.  Katalytische Hydrierung mit Rhodiumkomplexen, die dipamp-pyrphos-Hybridliganden enthalten† , 1993 .

[21]  D. Matt,et al.  A convenient synthesis of carbamoylmethylphosphines. X-ray structure of (diphenylphosphino)-N,N-diphenylacetamide , 1993 .

[22]  Y. Uozumi,et al.  Synthesis of optically active 2-(diarylphosphino)-1,1'-binaphthyls, efficient chiral monodentate phosphine ligands , 1993 .

[23]  R. Ziessel,et al.  Synthesis and coordination properties of novel polyfunctional phosphine ligands , 1993 .

[24]  T. Imamoto.  Synthesis and reactions of new phosphine - boranes , 1993 .

[25]  C. Mealli,et al.  Synthesis and reactivity of (η6-arene)(phosphino enolato)ruthenium(II) complexes, their coupling reaction with phenylacetylene, and thermal rearrangement to a phosphametallacyclopropane. X-ray crystal structures of {Ru[η3-CH=C(Ph)CH(PPh2)C(But)=O](p-cymene)}(PF6), of {Ru[η3-CH=C(Ph)C(Me)(PPh2)C(Et)= , 1993 .

[26]  A. Vasella,et al.  Synthesis and evaluation in asymmetric hydrogenation of carbohydrate-derived 1,3-bisphosphines , 1992 .

[27]  P. Pellon.  Phosphine-boranes in synthesis. Borane as an efficient protecting group in the preparation of functionalized phosphines , 1992 .

[28]  M. Sawamura,et al.  CATALYTIC ASYMMETRIC SYNTHESIS BY MEANS OF SECONDARY INTERACTION BETWEEN CHIRAL LIGANDS AND SUBSTRATES , 1992 .

[29]  A. Orpen,et al.  Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium and platinum: crystal structure of , 1992 .

[30]  Y. Uozumi,et al.  Catalytic asymmetric synthesis of optically active alcohols via hydrosilylation of olefins with a chiral monophosphine-palladium catalyst , 1992 .

[31]  A. Terfort.  Synthesis and Application of (3R,4R)-3,4-Bis(diphenylphosphino)tetrahydrofuran as Ligand for Asymmetric Hydrogenation of Acrylic Acids , 1992 .

[32]  J. Fiaud,et al.  2-hydroxyalkyl diphenylphosphines : biocatalytic resolution and use as ligands for transition-metal catalysts , 1991 .

[33]  E. Lindner,et al.  Coordination chemistry and catalysis with hemilabile oxygen-phosphorus ligands , 1991 .

[34]  S. D. Perera,et al.  Complexes including acetylides formed from 3-diphenylphosphinocamphor and platinum or palladium , 1991 .

[35]  Shengyong Zhang,et al.  A new approach to the synthesis of (−)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(diop) , 1991 .

[36]  W. Keim.  Nickel: An Element with Wide Application in Industrial Homogeneous Catalysis , 1990 .

[37]  W. Keim.  Nickel: Ein Element mit vielfältigen Eigenschaften in der technisch‐homogenen Katalyse , 1990 .

[38]  P. Pringle,et al.  TEMPLATE SYNTHESIS OF THE COORDINATED TRIPHOSPHORUS LIGANDS (PH2PCH2CRR'O)2PPH, R OR R' = H OR CH3 , 1989 .

[39]  P. Braunstein,et al.  β-Keto phosphines derived from ferrocene. Syntheses and structures of [Ph2PCH2C(O)(η5-C5H4)Fe(η5-C5H5)] (L1) and trans-[PdCl2L12] , 1989 .

[40]  H. Brunner,et al.  Synthesis of New Optically Active Bis- and Tris(phosphines) , 1989 .

[41]  D. Enders,et al.  Structure of a Chiral Lithium Azaenolate: Monomeric, Intramolecular Chelated Lithio‐2‐acetylnaphthalene‐SAMP‐hydrazone , 1988 .

[42]  M. Marsch,et al.  Struktur eines chiralen Lithium‐azaenolats: monomeres, intramolekular chelatisiertes Lithio‐2‐acetylnaphthalin‐SAMP‐hydrazon , 1988 .

[43]  H. Brunner,et al.  Synthesis of Optically Active Phosphanes via Sharpless Epoxidation , 1988 .

[44]  H. Brunner,et al.  Synthese optisch aktiver Phosphane via Sharpless-Epoxidierung , 1988 .

[45]  G. Wilke.  Beiträge zur nickelorganischen Chemie , 1988 .

[46]  G. Wilke.  Contributions to Organo‐Nickel Chemistry , 1988 .

[47]  P. Braunstein,et al.  Complexes of functional phosphines. 10. Palladium complexes with the ligands (diphenylphosphino)acetophenone, (Ph2PCHCOPh)- and Ph2PCHC(Ph)OPPh2. Crystal and molecular structure of cis-[PdCl2{Ph2PCH:C(Ph)OPPh2}] , 1986 .

[48]  Kazuhiko Sato,et al.  Phosphine oxides and lithium aluminum hydride-sodium borohydride-cerium(III) chloride: synthesis and reactions of phosphine-boranes , 1985 .

[49]  G. K. Anderson,et al.  Platinum(II) complexes of unsymmetrical, potentially bidentate ligands , 1984 .

[50]  D. Enders.  4 – Alkylation of Chiral Hydrazones , 1984 .

[51]  W. Keim.  Vor‐ und Nachteile der homogenen Übergangsmetallkatalyse, dargestellt am SHOP‐Prozeß , 1984 .

[52]  M. Peuckert,et al.  A new nickel complex for the oligomerization of ethylene , 1983 .

[53]  H. Brunner,et al.  Synthese von β-Diphenylphosphin-carbonyl-Verbindungen durch Umsetzung von Brommethyl-carbonyl-Verbindungen mit Diphenyl(trimethylsilyl)phosphin / Synthesis of β-Diphenylphosphine-carbonyl Compounds by Reaction of Bromomethyl-carbonyl Compounds with Diphenyl(trimethylsilyl)phosphine , 1982 .

[54]  J. Stille,et al.  Chiral 1,2-diphosphine ligands. Synthesis and application to rhodium-catalyzed asymmetric hydrogenations , 1982 .

[55]  H. Schmidbaur.  New phosphaneborane chemistry , 1980 .

[56]  E. Weiss,et al.  Die Chemie der H3B(CH3)2 P‐Gruppe: Ungewöhnliche Eigenschaften einfacher Standardverbindungen , 1979 .

[57]  H. Schmidbaur,et al.  Chemistry of the H3B(CH3)2P Group: Unusual Properties of Some Simple Reference Compounds , 1979 .

[58]  D. Enders,et al.  Asymmetrische Synthesen via metallierte chirale Hydrazone. Enantioselektive Alkylierung von cyclischen Ketonen und Aldehyden1 , 1979 .

[59]  E. J. Corey,et al.  Herstellung und synthetische Verwendung von metallierten Dimethylhydrazonen Regio‐ und stereoselektive Alkylierung von Carbonylverbindungen , 1978 .

[60]  M. T. Reetz,et al.  ber Aciditt und Olefinierungsreaktionen von a-(Diphenylphosphino)carbonylverbindungen , 1977 .

[61]  H. Mosher,et al.  Nuclear magnetic resonance enantiomer regents. Configurational correlations via nuclear magnetic resonance chemical shifts of diastereomeric mandelate, O-methylmandelate, and .alpha.-methoxy-.alpha.-trifluoromethylphenylacetate (MTPA) esters , 1973 .

[62]  H. Kagan,et al.  Asymmetric catalytic reduction with transition metal complexes. I. Catalytic system of rhodium(I) with (-)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, a new chiral diphosphine , 1972 .

[63]  D. Dull,et al.  .alpha.-Methoxy-.alpha.-trifluoromethylphenylacetic acid, a versatile reagent for the determination of enantiomeric composition of alcohols and amines , 1969 .

[64]  K. Ǐssleib,et al.  Alkali‐Phosphorverbindungen und ihr reaktives Verhalten, VI: Reaktionen der Alkaliphosphide, MePR2, mit äthylenoxyd , 1961 .

[65]  K. Ǐssleib,et al.  Alkali‐Phosphorverbindungen und ihr reaktives Verhalten, V. Darstellung von Carboxyphosphinen R2P‐[CH2]n‐CO2H , 1960 .