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WO1993012260A2 - Ligands asymetriques utiles pour les reactions formant des liaisons catalysees par metal de transition - Google Patents

Ligands asymetriques utiles pour les reactions formant des liaisons catalysees par metal de transition Download PDF

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Publication number
WO1993012260A2
WO1993012260A2 PCT/US1992/010386 US9210386W WO9312260A2 WO 1993012260 A2 WO1993012260 A2 WO 1993012260A2 US 9210386 W US9210386 W US 9210386W WO 9312260 A2 WO9312260 A2 WO 9312260A2
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Prior art keywords
ligand
chiral
carboxylic acid
aryl
transition metal
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PCT/US1992/010386
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WO1993012260A3 (fr
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Barry M. Trost
David L. Van Vranken
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Board Of Trustees Of The Leland Stanford Junio
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/416—2,5-Pyrrolidine-diones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/381—Phosphines, e.g. compounds with the formula PRnH3-n, with n = 0-3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention generally relates to use of ligands for transition metal catalyzed reactions, and more particularly relates to a new class of asymmetric ligands preferably derived from 2-diphenylphosphino- benzoic acid as an ester or amide from chiral alcohols and chiral amines.
  • transition metals in organic synthesis stems from their ability to orchestrate bond-forming and bond-breaking processes which fall outside the realm of traditional organic chemistry.
  • Such transition metal-mediated reactions offer the unique opportunity to allow asymmetric molecules to participate in a bond breaking and/or making process in an organized manner by coordinating to the active metal center.
  • the importance of absolute stereochemistry and the difficulty of obtaining homochiral compounds by traditional methods has provided the motivation for developing new methods for the creation of chirality.
  • Enantioselective catalysis in general hinges upon the ability to convert enantiotopic transition states into diastereotopic transition states by the introduction of complementary stereogenic centers into the active catalyst.
  • the energy difference between the diastereotopic transition states thus determines the enantioselectivity in the reaction.
  • Small energy differences between the two transition states translate into relatively large differences in enantiomeric excess.
  • the vast majority of unoptimized asymmetric metal-catalyzed reactions reported in the literature have enantiomeric excesses below 80%.
  • asymmetric ligands In enantioselective transition metal catalyzed reactions, the use of asymmetric ligands is essential (either as a temporary template to create a chiral complex or as a permanent part of the metal complex) since stereogenic metal centers cannot be readily derived from the chiral pool.
  • Phosphines play an important part in transition metal chemistry because of their ability to form stable transition metal complexes and to modify reactivity through both sterics and electronics.
  • a very large number of chiral phosphine ligands have been prepared, although only a small portion of them have gained popular use.
  • a representative sampling of some of the common chiral phosphine ligand designs that have been investigated are shown below.
  • 3,5-diol derivatives is directly applicable to the synthesis of prostanoids (see Kitamura et al., "Kinetic Resolution of 4-Hydroxy-2-cyclopentenone by Rhodium Catalyzed Asymmetric Isomerization", Tetrahedron Lett. , 1987, 28, 4719) and carbanucleosides that are potential anti-viral and anti-tumor compounds (such as carbovir and aristeromycin, the latter discussed by Trost et al., J. Am. Chem. Soc , 1988, 110 , 621 (1988).
  • a ligand is provided that is useful for transition metal catalyzed bond forming reactions and comprises a metal binding portion bound to a chiral scaffold.
  • the chiral scaffold is derived from an asymmetric alcohol or an asymmetric amine.
  • the metal binding portion has at least one metal binding moiety with the structure — C—Ar—P—Ar' 2
  • Ar and Ar' each is an aryl or a heteroaryl with a single ring or fused rings.
  • the metal binding portion and the chiral scaffold are preferably bound with two or three metal binding moieties for each chiral scaffold.
  • the chiral scaffold preferably is a C 2 symmetric diol or diamine.
  • a method for preparing ligands useful for transition metal catalyzed bond forming reactions comprises providing an aromatic carboxylic acid having a diarylphosphino or diheteroarylphosphino substituent on the aromatic ring, and forming an ester or an amide derivative of the carboxylic acid by coupling with a chiral diol or a chiral diamine in the presence of dicyclohexyl- carbodiimide.
  • a method for synthesizing cyclopentane analogs of carbohydrates comprises asymmetrically introducing heteroatoms around a cyclopentane nucleus of an intermediate while controlling the introduction by inducing an enantiomeric excess. Control is exercised by contacting the intermediate with a transition metal and a ligand for the transition metal.
  • the ligand has a metal binding portion bound to a chiral scaffold.
  • the chiral scaffold is derived from an asymmetric alcohol or an asymmetric amine.
  • the metal binding portion is an aryl carboxylic acid derivative or a heteroaryl carboxylic acid derivative with a diarylphosphino or diheteroarylphosphino substituent on the aryl or on the heteroaryl moiety.
  • the chirality of the ligand may be selected so as to correspond to the desired absolute stereochemistry induced in the transition metal catalyzed reaction.
  • Ligands of the invention can be easily and flexibly prepared over a broad spectrum of chiral scaffolds for high levels of asymmetric induction.
  • Inventive ligands preferably contain a plurality of metal binding sites and are capable of forming C 2 symmetrical complexes.
  • chiral diols useful for derivatizing 2-diphenylphosphinobenzoic acid to prepare ligands in accordance with the invention are mannitol and tartaric acid, with particularly effective ligands prepared from chiral diamines.
  • ligands in accordance with the present invention give enantiomeric excesses ("e.e.") of about 75% or greater when tested in a relatively difficult transition metal catalyzed bond forming, five membered ring reaction.
  • This e.e. test involves the ability of a chiral ligand to participate with palladium in a catalysis illustrated by Reaction 1 below.
  • Transition metal catalyzed bond forming reactions (with which ligands in accordance with the invention are useful) are well known in the art, and among the recent reviews describing such reactions are:
  • transition metal catalyzed bond forming reactions are those involving palladium.
  • One application of this invention is to form cyclopentane analogs of carbohydrates through use of the inventive ligands and palladium. Preparation of mannostatin A exemplifies this class.
  • Particularly preferred asymmetric ligands of the invention for transition metal catalyzed reactions are derived from 2-diphenyl- phosphinobenzoic acid (2-DPPBA) as ester or amide derivatives of chiral alcohols and chiral amines.
  • the 2-DPPBA may be derivatized with any of a wide variety of chiral alcohols or chiral amines, preferably by coupling in the presence of dicyclohexyl- carbodiimide (DCC), as illustrated by Reaction 2.
  • DCC dicyclohexyl- carbodiimide
  • While a derivatized 2-DPPBA is a particularly preferred manner of practicing the present invention, with 2-DPPBA forming the metal binding moiety of the inventive ligand, other aromatic carboxylic acids can be used so long as the aromatic carboxylic acid carries a diarylphosphino (or a diheteroarylphosphino) substituent.
  • the necessary phosphino substituent and the carbonyl substituent may be on an aryl or heteroaryl that is further substituted by a moderately or weakly activating or deactivating group, such as with an alkyl group (branched or unbranched) usually with not greater than about ten carbons, a halide, or an alkoxy (e.g.,
  • the single aryl ring exemplified by 2-DPPBA can be replaced with a fused aryl or heteroaryl ring, such as, for example, naphtha lene (optionally substituted as just described for the single aryl ring).
  • the necessary phosphino substituent and the carboxyl substituent can either be 1,2 on the one ring or can be 1,3 across the two rings.
  • the heteroatoms that can form the single or fused heteroaryl ring of the aromatic carboxylic acid from which the inventive ligands may be derived are nitrogen, oxygen, and sulfur.
  • suitable heteroaryl carboxylic acids on which the diarylphosphino (or diheteroarylphosphino) group can be substituted include compounds such as
  • X O, S, NR
  • the carboxyl group and the diphenylphosphino group are preferably in an ortho relationship, which serves best for the ligand function.
  • ligands of the invention have metal binding portion that is bound to a chiral scaffold.
  • the metal binding portion has at least one metal binding moiety (preferably two and sometimes three) with the Formula 1 structure:
  • Ar and Ar' each is an aryl or a heteroaryl with a single ring or fused rings.
  • An illustrative heteroaryl for Ar' is, for example, 2-furyl.
  • the "PAr' 2 " moiety will sometimes hereinafter be referred to as an "aromatic phosphino.”
  • the metal binding portion (or portions) and the chiral scaffold are preferably covalently bound.
  • Example A exemplifies the (known) preparation of the particularly preferred carboxylic acid precursor, 2-DPPBA.
  • Examples B and C give two alternate general procedures for the preparation of ligands from the 2-DPPBA in a coupling using DCC.
  • Examples 1-8 describe in detail the preparations of the ligands summarized in Table 1. The remaining examples then illustrate some uses of the inventive ligands.
  • silica gel was loaded onto a 4.3x14 cm column of silica gel and eluted with 50% ethyl acetate/hexanes (1 L) followed by 70% ethyl acetate/hexanes (500 mL).
  • reaction mixture was filtered through a 2 cm pad of celite (wetted with dichloromethane) and the filter cake was washed twice with an equal volume of dichloromethane. Solvent was removed in vacuo and the residue was chromatographed on silica gel.
  • Ligand (S)-(+)-6.24 white needles from dichloromethane/hexane), m.p. 114-116°C.
  • IR (neat film from CDCl 3 ) 3069, 3056, 3016, 3002, 2932, 2855, 1955(w), 1901(w), 1817(w), 1731(s), 1585, 1511, 1478, 1463, 1434, 1267, 1245, 1220, 1206, 1137, 1089, 1043, 908, 807, 742, 696, 649 cm -1 .
  • IR (neat film from CDCl 3 ) 3070, 3055, 2987, 2935, 2890, 1724 (s), 1585, 1478, 1463, 1434, 1381, 1372, 1245 (s), 1139, 1245(s), 1139, 1101, 1066, 1054, 909, 850, 745, 697 cm -1 .
  • Ligand 6.26 m.p. 125-127°C (plates from ether/dichloromethane).
  • IR (neat film from CDCl 3 ) 3069, 3056, 2866, 1955(w), 1890(w), 1815(w), 1722(s), 1585, 1478, 1463, 1435, 1377, 1312, 1266, 1249, 1224, 1140, 1111, 1058, 1027, 998, 909, 745, 731, 690 cm -1 .
  • Ligand (-)-6.27 white solid precipitated from dichloromethane with hexanes, m.p. 135-136°C.
  • IR (neat film from CDCl 3 ) 3410, 3326(b), 3071, 3046, 2979, 2937,. 2873, 1956 (w), 1889 (w), 1818 (w), 1733, 1653 (S), 1586, 1564, 1514 (s), 1459, 1154, 1122, 1091, 1071, 1046, 1028 cm -1 .
  • Ligand (+)-6.27 white solid precipitate from dichloromethane with hexanes.
  • Ligand 6.28 waxy solid precipitated from dichloromethane with hexanes, m.p. 80-120°C.
  • the ligand 6.29 is a particularly preferred embodiment of the invention when prepared from chiral diols because the chiral diol useful as the chiral scaffold in preparing inventive ligand 6.29 is readily derived from tartaric acid via tartrimide.
  • Preparation of the tartrimide from tartaric acid is known and is generally illustrated by Reaction 3 as follows:
  • the ligand 6.29 can have Bn as aryl or alkyl (such as, for example, lower alkyl) in addition to benzyl.
  • Bn aryl or alkyl (such as, for example, lower alkyl) in addition to benzyl.
  • IR (neat film from CDCl 3 ) 3066, 3031, 2957, 2929, 2830, 1952 (w), 1882 (w), 1813 (w), 1716 (s), 1586, 1495, 1478, 1463, 1455, 1434, 1361, 1310, 1268, 1252, 1141, 1106, 1057, 1027, 1002, 965, 909 cm -1 .
  • Ligand (+)-6.32 glass foam.
  • IR (neat film from CDCl 3 ) 3418, 3396, 3305(b), 3070, 3063, 3026, 1955 (w), 1905(w), 1885(w), 1818(w), 1652 (s), 1585, 1505(s), 1480, 1459, 1327, 1308, 1293, 1250, 1228, 1155, 1124, 1090, 1027, 909 cm -1 .
  • [ ⁇ ] 405 +211.2 ( ⁇ 3)°(c3.35, 26°C, dichloromethane).
  • C 2 -symmetrical complexes that is, the ligands which bind palladium with C 2 symmetry
  • ligand stereochemistry predicts product stereochemistry.
  • the stereogenic backbone of the inventive ligands has no direct interaction with the palladium-olefin moiety
  • the two otherwise independent triphenylphosphines defined by the chiral linkage, or scaffold serve to organize the aromatic rings into a chiral array and provide a direct relationship for absolute stereochemistry of the product from the catalysis.
  • Example 9 illustrates a general procedure for palladium catalysis with inventive ligands exemplified by chiral 2-(diphenylphosphino)benzoate esters and amides.
  • the black-purple slurry was stirred at room temperature until a homogeneous solution was obtained and then at 50°C for 10 minutes resulting in a clear, red-orange solution (0.05M in palladium).
  • the catalyst solution was then cooled to 0°C and the bis-carbamate solution was added dropwise.
  • the reaction was stirred at 0°C until thin layer chromatograph (50% ethyl, acetate/hexanes) . indicated complete consumption of bis-carbamate and then solvent was. removed in vacuo.
  • the resulting brown-orange oil was directly chromatographed on silica gel with 10-20% ethyl acetate/hexanes (gradient) to afford scalemic oxazolidinone.
  • Example 9 The Example 9 procedure was used for each of the inventive ligands reported in Table 1 for product yields up to 100% (through use of ligand 6.25 and ligand 6.31). Inventive ligands were used in the asymmetric synthesis of an intermediate for the synthesis of Mannostatin A (as we reported in Trost and Van Vranken, "A Flexible Strategy to Polyfunctional Cyclopentanes. A Synth ⁇ sis of Mannostatin A", J. of Am. Chem. Soc , 113 , 6317-6318 (1991).
  • Mannostatin A is a highly specific non-toxic inhibitor of ⁇ -D-mannosidase, and thus this glycosidase inhibitor has potential as an antiviral agent, as well as possibly an antimedistatic, anti-tumor proliferative, or an immunoregulatory agent. Mannosidase inhibitors, in particular, have been suggested as potential anti-HIV agents.
  • Example 10 illustrates the retrosynthetic analysis for the chemo-, regio-, and diastereoselec tivity of introduction of three different heteroatom functions on each and every carbon of a Gyclopentane, and thus is a procedure that may be used to make carbanucleoside intermediates asymmetrically since the cyclopentane is a key intermediate towards pseudomono- saccharides.
  • the best mode contemplated for carrying out this invention is building substituted five membered carbocyclic rings with varying substituted patterns with high enantioselectivity.
  • Example 10 illustrates use of the invention to make a carbanucleoside in which use of inventive ligand 6.28 permitted the excellent enantiomericnexcess of 96%.
  • inventive ligand permits highly flexible strategies for the controlled introduction of heteroatoms around a cyclopentane nucleus.
  • IR (KBr) 3300, 3150, 1744, 1676, 1607, 1569, 1475, 1439, 1331, 1305, 1274, 957.

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Abstract

Ligands utiles pour les réactions formant des liaisons catalysées par métal de transition, comprenant une partie de liaison du métal renfermant au moins une fraction de liaison du métal ayant la structure (I) dans laquelle Ar et Ar' représentent chacun un aryle ou un hétéroaryle. On peut préparer ces ligands en utilisant un acide carboxylique aromatique comprenant un substituant diarylphosphino ou dihétéroarylphosphino sur le cycle aromatique, et en formant un ester ou un dérivé d'amide de l'acide carboxylique par couplage avec un diol chiral ou une diamine chirale. Ces ligands permettent de mettre en ÷uvre des stratégies souples servant à construire de manière enantiocontrôlée des composés carbocycliques à cinq membres présentant des schémas de substitution variables et une forte énantiosélectivité.
PCT/US1992/010386 1991-12-09 1992-12-02 Ligands asymetriques utiles pour les reactions formant des liaisons catalysees par metal de transition WO1993012260A2 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0782577A4 (fr) * 1994-09-19 1998-01-07 Univ Leland Stanford Junior Ligands asymetriques utiles pour des reactions de formation de liaisons catalysees par des metaux de transition et leur utilisation dans des reactions impliquant des epoxydes
WO1999051614A1 (fr) * 1998-04-02 1999-10-14 Chirotech Technology Limited Preparation de ligands de phosphine
WO2000000498A1 (fr) * 1998-06-30 2000-01-06 Chirotech Technology Limited Preparation d'arylphosphines
WO2000008032A1 (fr) * 1998-08-06 2000-02-17 Symyx Technologies, Inc. Ligands catalytiques utilises dans des reaction de couplage croise
US6225487B1 (en) 1998-04-17 2001-05-01 Symyx Technologies, Inc. Ancillary ligands and metal complexes, catalysts and compositions using same and methods of testing
US6265601B1 (en) 1998-08-06 2001-07-24 Symyx Technologies, Inc. Methods for using phosphine ligands in compositions for suzuki cross-coupling reactions
US6268513B1 (en) 1998-08-06 2001-07-31 Symyx Technologies, Inc. Phosphine ligands metal complexes and compositions thereof for cross-coupling reactions
US6320068B1 (en) 1998-06-30 2001-11-20 Chirotech Technology, Ltd. Preparation of arylphosphines
KR100359190B1 (ko) * 1997-12-15 2002-11-01 타운샌드 엔지니어링 컴파니 압출된 소시지 가닥을 경화시키기 위한 염수 제형
EP1398319A1 (fr) * 2002-09-12 2004-03-17 Bayer Chemicals AG Composés monophosphore chiraux et leurs complexes de metaux transitoires

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209468A (en) * 1977-03-28 1980-06-24 The Procter & Gamble Company Triaryl-phosphine compounds
JPS62178594A (ja) * 1986-02-01 1987-08-05 Takasago Corp 新規ホスフイン化合物

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0782577A4 (fr) * 1994-09-19 1998-01-07 Univ Leland Stanford Junior Ligands asymetriques utiles pour des reactions de formation de liaisons catalysees par des metaux de transition et leur utilisation dans des reactions impliquant des epoxydes
KR100359190B1 (ko) * 1997-12-15 2002-11-01 타운샌드 엔지니어링 컴파니 압출된 소시지 가닥을 경화시키기 위한 염수 제형
WO1999051614A1 (fr) * 1998-04-02 1999-10-14 Chirotech Technology Limited Preparation de ligands de phosphine
US6486347B2 (en) 1998-04-02 2002-11-26 Chirotech Technology, Ltd. Preparation of phosphine ligands
US6124476A (en) * 1998-04-17 2000-09-26 Symyx Technologies, Inc. Catalyst ligands, catalyst compositions, catalyst metal complexes and processes for cross-coupling aromatic boron compounds with aromatic halogens or perfluoroalkylsulfonates
US6225487B1 (en) 1998-04-17 2001-05-01 Symyx Technologies, Inc. Ancillary ligands and metal complexes, catalysts and compositions using same and methods of testing
WO2000000498A1 (fr) * 1998-06-30 2000-01-06 Chirotech Technology Limited Preparation d'arylphosphines
US6320068B1 (en) 1998-06-30 2001-11-20 Chirotech Technology, Ltd. Preparation of arylphosphines
WO2000008032A1 (fr) * 1998-08-06 2000-02-17 Symyx Technologies, Inc. Ligands catalytiques utilises dans des reaction de couplage croise
US6265601B1 (en) 1998-08-06 2001-07-24 Symyx Technologies, Inc. Methods for using phosphine ligands in compositions for suzuki cross-coupling reactions
US6268513B1 (en) 1998-08-06 2001-07-31 Symyx Technologies, Inc. Phosphine ligands metal complexes and compositions thereof for cross-coupling reactions
EP1398319A1 (fr) * 2002-09-12 2004-03-17 Bayer Chemicals AG Composés monophosphore chiraux et leurs complexes de metaux transitoires

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