WO2000011008A1 - Asymmetric catalysis based on chiral phospholanes - Google Patents

Asymmetric catalysis based on chiral phospholanes Download PDF

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Publication number
WO2000011008A1
WO2000011008A1 PCT/US1999/018932 US9918932W WO0011008A1 WO 2000011008 A1 WO2000011008 A1 WO 2000011008A1 US 9918932 W US9918932 W US 9918932W WO 0011008 A1 WO0011008 A1 WO 0011008A1
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Prior art keywords
alkyl
aryl
substituted
divalent
compound
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PCT/US1999/018932
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English (en)
French (fr)
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Xumu Zhang
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The Penn State Research Foundation
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Priority claimed from US09/377,065 external-priority patent/US6337406B1/en
Application filed by The Penn State Research Foundation filed Critical The Penn State Research Foundation
Priority to CA002340943A priority Critical patent/CA2340943A1/en
Priority to JP2000566281A priority patent/JP2002523419A/ja
Priority to AU54929/99A priority patent/AU5492999A/en
Priority to EP99941237A priority patent/EP1105400A1/de
Publication of WO2000011008A1 publication Critical patent/WO2000011008A1/en

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Definitions

  • This invention relates to chiral phospholanes derived from natural products, and asymmetric catalysis using these phospholanes.
  • the ligands DuPhosTM and BPE have been used effectively for certain asymmetric hydrogenation reactions. See U.S. Patent Nos. 5,329,015; 5,202,493; and 5,329,015; Burk, M.J., J. Am. Chem. Soc. (1991) 113, 8518; Burk, M.J., J. Am. Chem. Soc. (1993) 115, 10125; Burk, M.J., J. Am. Chem. Soc. (1996) 118, 5142. These ligands, however, are not effective for some other asymmetric reactions. Moreover, synthesis of these ligands can be difficult, involving a tedious Kolbe reaction. Also, several liquid DuPhosTM BPE ligands are air-sensitive and therefore difficult to handle.
  • One aspect of the invention is a ligand of formula A, , B, B', C, C, D, or D', or the corresponding enantiomer:
  • Another aspect of the invention is a compound of the formula E:
  • Another aspect of the invention is a catalyst including one of the compounds A-E above, wherein the compound is in the form of a complex with a transition metal.
  • Another aspect of the invention is a process for preparing a compound of formula B, by reacting a compound of formula B x with a phosphine:
  • Another aspect of the invention is a process that includes subjecting a substrate to an asymmetric reaction in the presence of one of the above-described ligands, wherein said asymmetric reaction is a hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels- Alder, Aldol, Heck, [m + n] cycloaddition, or Michael addition reaction.
  • said asymmetric reaction is a hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels- Alder, Aldol, Heck, [m + n] cycloaddition, or Michael addition reaction.
  • one advantage of the invention is in providing chiral ligands that can be made in large scale from inexpensive natural products such as D-mannitol or tartaric acids.
  • Another advantage is in providing new chiral ligands A'-D' in FIG. 3, in which the relative configuration of the four stereogenic centers around the phospholane differs from A-D.
  • Yet another advantage is in providing chiral ligands that are solid and/or more air-stable due to added functional groups, and are more easily handled compared to air-sensitive liquids such as DuPhosTM/BPE ligands. Yet another advantage is in providing chiral ligands that have functional groups on the phospholanes that can be key stereochemistry-defining groups, such as a hemilabile anchor, a hydrogen bonding source, or a cation binding site through a crown ether. Yet another advantage is in providing chiral ligands that have additional functional groups on the phospholanes with water-soluble properties and a convenient site to link a polymer support.
  • Yet another advantage of the invention is in providing catalysts for a variety of asymmetric reactions such as hydrogenation, hydride transfer reaction, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels- Alder reaction, Aldol reaction, Heck reaction, Baylis-Hillman reaction and Michael addition can be explored based on these innovative ligand systems.
  • asymmetric reactions such as hydrogenation, hydride transfer reaction, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels- Alder reaction, Aldol reaction, Heck reaction, Baylis-Hillman reaction and Michael addition can be explored based on these innovative ligand systems.
  • Yet another advantage of the invention is in providing a variety of methods to make both enantiomers of chiral phosphines.
  • D-mannitol other chiral pool materials such as D and L-tartaric acids can also be used as suitable starting materials for ligand synthesis.
  • D and L-tartaric acids can also be used as suitable starting materials for ligand synthesis. Only one phospholane enantiomer can be conveniently obtained using D-mannitol as the starting material while both phospholane enantiomers can be easily obtained when using D and L-tartaric acids for the ligand synthesis.
  • FIG. 1 shows new chiral ligands A, A B, B', C, C, D, and D' of the invention.
  • FIGs. 2A-2F shows the structure of ligand examples LI to L32.
  • FIGs. 3A-3C illustrate syntheses of ligands LI to L32.
  • FIGs. 4A-4C show syntheses of some chiral 1,4-diols.
  • % ee enantiomeric excess, (%S - %R)/(%S + %R) or (%R - %S)/(%S + %R) acac: acetylacetonate
  • Bn benzyl COD: 1,5-cyclooctadiene
  • HMPA hexamethylphosphoramide
  • the chiral ligands of the present invention may contain alkyl and aryl groups.
  • alkyl is meant any straight, branched, or cyclic alkyl group.
  • the number of carbons in the alkyl group is not particularly limited.
  • alkyl refers to Cl- C20, more preferably C1-C8, even more preferably C1-C4 alkyl groups.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, and cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and isomers of heptyl, octyl, and nonyl.
  • Alkyl groups may be substituted without particular restriction, provided that the substituents do not have an adverse effect on the asymmetric reaction, and are inert to the reaction conditions or are thereby converted in a desirable manner.
  • substituents include, but are not limited to, aryl, heterocyclo, alkoxy, halo, haloalkyl, amino, alkylamino, dialkylamino, nitro, amido, and carboxylic ester groups, and any suitable combination thereof.
  • aryl any aromatic or heteroaromatic ring, including such rings fused to other aliphatic, aromatic or heteroaromatic rings.
  • aromatic rings include, but are not limited to, phenyl, naphthyl, anthryl, fluorenyl, indenyl, and phenanthryl.
  • Heteroaromatic rings may contain one or more heteroatoms, preferably one or more atoms of nitrogen, oxygen, or sulfur.
  • heteroaromatic rings include, but are not limited to, pyrrole, pyridine, quinoline, isoquinoline, indole, furan, and thiophene.
  • Aryl groups may be substituted without particular restriction, provided that the substituents do not have an adverse effect on the asymmetric reaction, and are inert to the reaction conditions or are thereby converted in a desirable manner.
  • substituents include, but are not limited to alkyl, aryl, heterocyclo, alkoxy, halo, haloalkyl, amino, alkylamino, dialkylamino, nitro, amido, and carboxylic ester groups, and any suitable combination thereof.
  • the optical purity of the ligand is preferably at least about 85% ee, more preferably at least about 90% ee, more preferably at least about 95% ee, even more preferably at least about 98% ee, and even more preferably about 100% ee.
  • a chiral ligand can exist as two enantiomers of opposite configuration.
  • a person skilled in the art will recognize that for any given asymmetric reaction, each enantiomer will produce products of opposite configuration from the other, but with the same conversion and optical purity.
  • ligand and product structures are shown for one enantiomer for convenience.
  • the disclosure also applies to the corresponding enantiomers of opposite configuration, and a person skilled in the art can select the appropriate enantiomer to achieve the desired product configuration.
  • FIG. 1 shows several classes of chiral phospholanes (A, B, C, D, and A', B', C ⁇ D').
  • A, B, C, D, and A', B', C ⁇ D' is in the inversion of two chiral centers in the middle of the rings.
  • enantiomers are also included, which can be made through different chiral pools.
  • a and A' are chiral bidentate phospholanes with four chiral centers.
  • B and B' are chiral bidentate phospholanes with four chiral centers and linked by a ring in the middle of five membered rings.
  • C, D, C, D' are monophospholanes.
  • Ligand LI (A) has a benzyl protecting group on the two center hydroxyl groups while ligand L3 has a hydroxyl group.
  • Ligand L2 belongs to class B' with a cyclic ketyl in the center.
  • Ligands LI -LI 3 contain bridging groups such as CH 2 CH 2 , benzene, ferrocene, biaryl, binaphthyl groups.
  • Ligands LI 4- L17 are linked to a polymer backbone.
  • Ligands L18-L21 have water soluble groups. In ligands L22-L25, an 18-crown-6 group was introduced.
  • Ligands L26-L27 are monophospholanes containing a variety of groups.
  • Ligands L30 - L32 have additional groups as substituents of aryls; some will lead to hemilabile ligands.
  • One embodiment of the invention is a compound of formula A, A', B, B', C, C, D, or D', or the corresponding enantiomer:
  • R and R 2 are aryl, alkyl, alkyl aryl, or aryl alkyl, which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, diphenylphosphino, or chiral oxazolino groups;
  • R 1 can be H, alkyl, silane, aryl, a water soluble unit, or a linked polymer chain or inorganic support;
  • the ring component 0 O represents a protected diol, a crown ether linkage, -O-alkyl-O- wherein the alkyl group is linked to a polymer, or -O-(CH 2 CH 2 - O) n - wherein the methylene groups are optionally substituted by C1-C8 alkyl; and
  • i Bridge may be:
  • n is an integer ranging from 1 to 8; -(CH 2 ) n X(CH 2 ) m - wherein n and m are each integers, the same or different, ranging from 1 to 8, and X is O, S, NR 4 , PR 4 , AsR 4 , SbR 4 , divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group, or divalent fused heterocyclic group, wherein R 4 is hydrogen, aryl, alkyl, substituted aryl or substituted alkyl groups; or
  • 1,2-divalent phenyl, 2,2'-divalent 1,1'biphenyl or 2,2'-divalent 1,2'binapthyl or ferrocene each of which may be substituted with aryl, C1-C8 alkyl, F, Cl, Br, I, COOR 5 , SO 3 R 5 , PO 3 R 5 2 , OR 5 , SR ⁇ NR 5 2 , PR 5 2 , AsR 5 2 , or SbR 5 2 , wherein: the substitution on 1 ,2-divalent phenyl, the ferrocene or biaryl bridge can be independently halogen, alkyl, alkoxyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl, alkynyl, or sulfonic acids; and
  • R 5 is hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, or C1-C8 perfluoroalkyl, aryl; substituted aryl; arylalkyl; ring-substituted arylalkyl; or -CR 3 2 (CR 3 2 ) q X(CR 3 2 ) p R 1 wherein q and p are integers, the same or different, ranging from 1 to 8; R 3 is an aryl, alkyl, substituted aryl and substituted alkyl group; and R 1 and X are as defined above.
  • the counterion for water soluble units bearing a charge include, but are not limited to, metals such as alkali and alkaline earth metals, and halogens and Otf.
  • the polymer may be any polymer or copolymer, preferably polystyrene or a copolymer of styrene and a substituted vinyl monomer, polyacrylate, PEG or MeO-PEG, or dendritic polymers of polyesters or polyenamides.
  • the preceding also applies to the ring component O ⁇ O as -O-alkyl-O- wherein the alkyl group is linked to a polymer.
  • R 1 is a linked inorganic support
  • examples of inorganic supports include, but are not limited to, silica or zeolites.
  • the ring component O ⁇ O is a protected diol
  • a person of skill in the art will recognize that any number of the diol protecting group may be used, e.g., those described in Greene and Wuts, Protective Groups in Organic Synthesis, 1991, John Wiley & Sons, and MacOmie, Protective Groups in Organic Chemistry, 1975, Plenum Press, the entire contents of which are incorporated herein by reference.
  • a suitable diol protecting group may be deprotected under conditions that do not significantly degrade the rest of the molecule. Examples of diol protecting groups include, but are not limited to acetals and ketals.
  • the invention is a compound of formula A or A', or the corresponding enantiomer.
  • R is methyl, ethyl, or benzyl
  • R' is hydrogen or benzyl
  • is -(CH 2 ) n - where n is an integer ranging from 1 to 3, 1,2-divalent phenyl; 2,2'-divalent 1,1'biphenyl, 2,2'-divalent 1,2'binapthyl, or ferrocene, each of which may be substituted with alkyl having 1-3 carbon atoms; or OR 5 , wherein R 5 is methyl or ethyl.
  • Examples of the compound of formula A or A' include, but are not limited to LI, L3-L5, L7-L8, L10-L12, and L18-L21, and the corresponding enantiomers, and the compound of formula 2 below and its enantiomer.
  • the invention is a compound of formula B or B', or the corresponding enantiomer.
  • R is C1-C4 alkyl, unsubstituted or substituted by phenyl or
  • R 5 is C1-C2 alkyl
  • the ring component 0 ⁇ 0 is -O-CR a R b -O-
  • R is hydrogen or C1-C4 alkyl and R b is an alkyl or aryl linker attached to a polymer.
  • Examples of the compound of formula B or B' include, but are not limited to L2, L6, L9, L13, L14-L17, and L22-L25, and the corresponding enantiomers, and the compound of formula 3 below and its enantiomer:
  • the invention is a compound of formula C, D, C, or D', or the corresponding enantiomer.
  • R is methyl, ethyl, or benzyl;
  • R' is hydrogen or benzyl;
  • R 2 is o-X-phenyl wherein X is a carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, diphenylphosphino, or chiral oxazolino group; and the ring component 0 ⁇ 0 is -O-CR a R b -O-, wherein R a and R b are independently hydrogen or
  • Examples of the compound of formula B or B' include, but are not limited to structures L26-L32, and the corresponding enantiomers, and the compound of formula 1 below and its enantiomer:
  • Another embodiment of the invention is a compound of formula E or the corresponding enantiomer.
  • R and R 9 are aryl, C1-C8 alkyl, C1-C8 alkyl aryl, or aryl C1-C8 alkyl, which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, diphenylphosphino, or chiral oxazolino groups; and
  • R is C1-C4 alkyl and R 9 is C1-C4 alkyl or phenyl.
  • Another embodiment of the invention is a catalyst including any of the compounds described in the embodiments above, wherein the compound is in the form of a complex with a transition metal.
  • any transition metal may be used.
  • the transition metal is a Group VIII transition metal. More preferably, the transition metal is rhodium, iridium, ruthenium, nickel, or palladium.
  • the compound is in the form of a complex with Pd 2 (DBA) 3 , Pd(OAc) 2 ; [Rh(COD)Cl] 2 , [Rh(COD) 2 ]X, Rh(acac)(CO) 2 ; RuCl 2 (COD), Ru(COD)(methylallyl) 2 , Ru(Ar)Cl 2 , wherein Ar is an aryl group, unsubstituted or substituted with an alkyl group; [Ir(COD)Cl] 2 , [Ir(COD) 2 ]X; or Ni(allyl)X; wherein X is a counterion.
  • the counterion X may generally be any suitable anion for use in asymmetric synthesis.
  • suitable counterions include, but are not limited to, halogen ions (including Cl ⁇ , Br ⁇ , and I ⁇ ), BF 4 - ClO 4 ⁇ SbF 6 ⁇ , CF 3 SO 3 - BAr 4 ⁇ (wherein Ar is aryl), and Otf- (trifluoromethanesulfonate).
  • X is BF 4 , ClO 4 , SbF 6 , or CF 3 SO 3 .
  • the catalyst comprises Ru(RCOO) 2 (diphosphine), RuX 2 (diphosphine), Ru(methylallyl) 2 (diphosphine), or Ru(aryl group)X 2 (diphosphine), and X is halogen.
  • Another embodiment of the invention is a process including subjecting a substrate to an asymmetric reaction in the presence of a catalyst comprising a chiral ligand according to claim 1 , wherein said asymmetric reaction is a hydrogenation, hydride transfer, hydrosilylation, hydroboration, hydrovinylation, olefin metathesis, hydroformylation, hydrocarboxylation, allylic alkylation, cyclopropanation, Diels- Alder, Aldol, Heck, [m + n] cycloaddition, or Michael addition reaction.
  • the process includes asymmetric hydrogenation of a ketone, imine, enamide, or olefin.
  • Another embodiment of the invention is a process for preparing a compound of formula B, comprising reacting a compound of formula B x with a phosphine:
  • the phosphine is H 2 PH Bridge ⁇ )-PH 2 ;
  • R is aryl, alkyl, alkyl aryl, or aryl alkyl, which may be substituted with carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkylamino, diphenylphosphino, or chiral oxazolino groups;
  • the ring component 0 ⁇ 0 represents a protected diol, a crown ether linkage, or -O-CH 2 CH 2 ) n -O- wherein n is an integer ranging from 1 to 8 and the methylene groups are optionally substituted by alkyl or linked to a polymer;
  • I Bridge may be:
  • n is an integer ranging from 1 to 8.
  • n, m are each integers, the same or different, ranging from 1 to 8; or
  • 1,2-divalent phenyl, 2,2'-divalent 1,1 'biphenyl or 2,2'-divalent 1,2'binapthyl or ferrocene each of which may be substituted with aryl or substituted aryl, or alkyl having 1-8 carbon atoms, heteroatom groups such as F, Cl, Br, I, COOR 5 , SO 3 R 5 , PO 3 R 5 2 , OR 5 , SR 5 , NR 5 2 , PR 5 2 , AsR 5 2 , or SbR 5 2 , wherein: the substitution on 1,2-divalent phenyl, the ferrocene or biaryl bridge can be independently halogen, alkyl, alkoxyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl, akkynyl, or sulfonic acids; and R 5 is hydrogen, C1-C8 alkyl, C1-C8 fluoroalkyl, or C1-C8
  • R is C1-C4 alkyl; the ring component 0 ⁇ 0 represents a protected diol; and I Bridge [ is unsubstituted or substituted 1,2-divalent phenyl. More prefarbly,
  • R is methyl or ethyl
  • the ring component O O is -O-C(CH 3 ) 2 -O-
  • Bridge is unsubstituted 1 ,2-divalent phenyl.
  • FIGs. 3A-3C show several pathways for the synthesis of compounds shown in FIGs. 2A-2F.
  • the chiral 1,4-diols used in the synthesis of ligands L1-L32 can be derived from D-mannitol and related compounds. A number of these diols have been reported in the literature.
  • the procedure for the synthesis of LI (A), L3(A) and L8 (A') is outlined in FIGs. 3A-3B; key intermediates L35 and L35' have been reported in the literature (Poitout, L.; Tetrahedron Letter (1994) 35, 3293).
  • the epoxide opening step from L35 to L37 in FIG. 3A has also been reported (Nugel, S. et al J. Med.
  • 18-crown-6 or water soluble groups can be linked to form compounds such as L19 (A) or L25 (B), as shown in FIGs. 2D and 2E, respectively.
  • FIGs. 4A-4C outline some useful synthetic procedures, which was recently disclosed in the literature. Instead of using D-mannitol as the starting material, which can only lead to one enantiomer of the chiral phosphine, preparation of chiral diols from either D or L-tartaric ester can result in formation of either of two enantiomers. Using these reported procedures (Nugel, S. et al. J. Med. Chem. (1996) 39, 2136; Colobert, F. J. Org. Chem. (1998) 63, 8918; and Iwasaki, S. Tetrahedron Lett. (1996) 37, 885), several chiral 1,4-diols can be obtained, as shown in FIGs. 4A-4C.
  • hydroxyl phosphine ligands 1, 2, and 3 were synthesized successfully in high yield using similar procedures. They are white solids.
  • the synthetic route is exemplified below.
  • Compound 10 is a nice colorless crystal and can be recrystallized from ethyl ether and methanol.
  • Compound 2 was used directly after removal of the reaction solvent without any purification.
  • An advantage of this route is that there is no need to run column chromatography for purification.
  • Compound 14 is a colorless crystal and can be recrystallized from ethyl ether and methanol.
  • the cyclic sulfate 15 was also made from the corresponding alcohol, which was synthesized in the same procedure to make 12.
  • Ligand 16 can be made in a similar manner using the same procedure as for the synthesis of 2 and 3.
  • Compound 18 was prepared by stirring 1 and phenylboronic acid in methylene chloride. After removal of the solvent, it was used directly in asymmetric reaction.
  • Compound 21 was prepared from known cyclic sulfate 20. Several chiral monophospho lanes from D-mannitol (e.g., 19, 21) are made and many methods cleave the protecting groups to give hydroxyl phospholane 1. The iso-propylene group in 19 was smoothly removed by an acid catalyzed hydrolysis. However, the borane adduct of 21 was just selectively debenzylated when BC1 3 or BF 3 .Et 2 O was used as the reagent to give the derivatives bearing one hydroxyl and one benzyl ether group. Hydrogenation of 21 using Pd/C catalyst does not give the desired hydroxyl phospholane product 1.
  • the corresponding phosphine oxide of 21 also gave selectively debenzylated products under mild hydrogenation conditions (10 % Pd(OH) 2 /C).
  • the hydrogenation reaction done under high temperature (50 °C) and H 2 pressure (40 atm) not only cleaved the benzyl ether but also reduced the phenyl group to a cyclohexyl group.
  • n-BuLi 1.6 M solution in n-hexane, 2.5 mL, 4.0 mmol
  • the color of the reaction mixture changed from orange yellow to red, and then decolorized to colorless.
  • the residue was dissolved in 40 mL of ethyl ether, and 30 mL of brine was added. The aqueous layer was then washed with 3 x 30 mL ethyl ether. The combined organic layers were dried over Na 2 SO 4 and concentrated to afford a colorless oil.
  • This oil can be further purified by a short silica gel column eluted with hexane/ether (9:1), "H NMR (CDC1 3 ): ⁇ 7.72-7.27 (m, 5H, aromatic), 4.60-4.32 (m, 2H), 2.70-2.51 (m, 2H), 1.52 (s, 6H), 1.38-1.32 (m, 3H), 0.70-0.52(m, 3H). 31 P NMR (CDC13): ⁇ 50.2 ppm.
  • Phosphine 19 obtained above was dissolved in 50 mL methanol and 2 mL of water. To this solution, 0.05 mL of methanesulfonic acid was added and the resulting mixture was refluxing for 10 h. The solvent was removed under reduced pressure and the residue was dissolved in 50 mL of methylene chloride. 30 mL of aq NaHCO 3 was added and the two layers were separated. The aqueous layer was washed with 3 x 40 mL of methylene chloride. The combined organic layers were dried over Na 2 SO 4 and concentrated to give a white solid, compound 1.
  • n-BuLi 1.6 M n-hexane solution, 1.25 mL, 2.0 mmol
  • n-BuLi 1.6 M solution in n-hexane, 11.0 mL, 17.5 mmol
  • the reaction mixture was stirred for additional 20 h at room temperature.
  • the residue was dissolved in 50 mL of ethyl ether, and 50 mL of brine was added.
  • the aqueous layer was then washed with 3 x 40 mL ethyl ether.
  • the combined organic layers were dried over Na 2 SO 4 and concentrated to afford a colorless crystal. This crystal was further recrystallized from ether/methanol.
  • Phosphine 10 obtained above was disolved in 100 mL of methanol and 2 mL of water. 0.1 mL of methanesufonic acid was added and the resulting mixturing was refluxing for 10 h. After removal of the solvent the residue was passed through a short plug of silica gel eluted with ethyl acetate/methanol (95:5) to give compound 2 as a white solid.
  • Phosphine 14 was prepared using the similar procedure for 10 and recrystallized from ethyl ether/methanol as a colorless crystal.
  • EXAMPLE 8 General Procedure for the Baylis-Hillman Reaction The mixture of 4-pyridinecarbonaldehyde (1 mmol) and 1 mL of methyl acrylate was degassed three times by a freeze-thaw method, and then the resulting solution was transferred into another Schlenk tube containing 10% catalyst. The solution was stirred at room temperature for some time and the methyl acrylate was removed under vaccm. The residue was purified by a flash chromatograph eluted with hexanes/ethyl acetate (1 :2). The enantiomeric excess was measured by capillary GC.
  • NHAc H 2 (3 atm), CH 3 OH, rt, 12 h NHAc

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WO2002048161A1 (en) * 2000-12-13 2002-06-20 Warner-Lambert Company Llc P-chirale bisphospholane ligands, their transition metal complexes
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US6855847B2 (en) 2001-07-24 2005-02-15 Takasago International Corporation Process for producing optically active amide from α β- unsaturated amide derivative in the presence of transition metal complex containing phosphine-phosphorane compound and transition metal
EP1905511A3 (de) * 2001-11-26 2010-01-27 INVISTA Technologies S.à.r.l. Phosphorhaltige Zusammensetzung und ihre Verwendung bei Hydrocyanierungs-, Isomerisierungs- und Hydroformylierungsreaktionen
EP1318156A1 (de) 2001-12-10 2003-06-11 Takasago International Corporation Neue asymmetrische Phosphin-Ligande
US6624320B2 (en) 2001-12-10 2003-09-23 Takasago International Corporation Asymmetric phosphine ligand
US6730629B2 (en) 2001-12-10 2004-05-04 Takasago International Corporation Asymmetric phosphine ligand
EP1864989A1 (de) * 2005-03-29 2007-12-12 Meiji Seika Kaisha Ltd. Verfahren zur herstellung von l-2-amino-4-(hydroxymethylphosphinyl)butansäure
EP1864989A4 (de) * 2005-03-29 2010-06-23 Meiji Seika Kaisha Verfahren zur herstellung von l-2-amino-4-(hydroxymethylphosphinyl)butansäure
WO2006116344A3 (en) * 2005-04-22 2007-05-18 Dow Global Technologies Inc Asymmetric hydroformylation process
WO2006116344A2 (en) * 2005-04-22 2006-11-02 Dow Global Technologies Inc. Asymmetric hydroformylation process
CN113603691A (zh) * 2021-08-12 2021-11-05 连云港冠昕医药科技有限公司 L-5-甲基四氢叶酸钙的制备工艺
CN114085251A (zh) * 2021-11-02 2022-02-25 中国人民解放军空军军医大学 一类手性二茂铁-螺环骨架双膦配体及其制备方法
CN114085251B (zh) * 2021-11-02 2024-01-19 中国人民解放军空军军医大学 一类手性二茂铁-螺环骨架双膦配体及其制备方法

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