[go: up one dir, main page]

WO2018189107A1 - Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation - Google Patents

Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation Download PDF

Info

Publication number
WO2018189107A1
WO2018189107A1 PCT/EP2018/059021 EP2018059021W WO2018189107A1 WO 2018189107 A1 WO2018189107 A1 WO 2018189107A1 EP 2018059021 W EP2018059021 W EP 2018059021W WO 2018189107 A1 WO2018189107 A1 WO 2018189107A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
stereoisomer
mixture
transition metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2018/059021
Other languages
English (en)
Inventor
Werner Bonrath
Zheng-Chuan FENG
Jonathan Alan Medlock
Kun Peng
Zhibin Zhu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to CN201880023975.2A priority Critical patent/CN110494439B/zh
Publication of WO2018189107A1 publication Critical patent/WO2018189107A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07F9/547—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
    • C07F9/65525—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 seven-(or more) membered ring
    • C07F9/65527—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 seven-(or more) membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses

Definitions

  • the present invention is related to chemical products and processes for preparation thereof.
  • the present invention is related to a new chiral biphenyl diphosphine ligand, the intermediate for the preparation of the ligand, and the processes for the preparation thereof.
  • the present invention is also related to a chiral transition metal catalyst containing the new chiral biphenyl diphosphine ligand of the present invention and the use of the chiral transition metal catalyst of the present invention in asymmetric reactions.
  • Asymmetric catalysis is one of the most powerful methods for accessing a wide range of enantiomerically enriched compounds through the action of a chiral catalyst in a variety of asymmetric reactions.
  • Highly promising candidates for asymmetric synthesis are transition metal complexes bearing chiral ligands.
  • chiral ligands employed in asymmetric synthesis only a few have found a practical application in the manufacture of chiral molecules by the chemical and pharmaceutical industry.
  • BINAP is one of frequently used chiral ligands.
  • BINAP has been shown to be highly effective for many asymmetric reactions (Noyori and Takaya, Acc. Chern. Res., 1990,23,345; and Olkuma et al., Am. Chern. Soc, 1998, 120, 13529).
  • Related axially dissymmetric ligands, such as MeO-BIPHEP and BIPHEMP have also been employed in a number of asymmetric reactions (Schmid et al., Pure &Appl. Chern., 1996,68,131; Foricher, Heiser and Schmid, U.S. Pat. No. 5,302,738; Michel, European Patent Application 0667350 Al; and Broger et al., WO 92/16536).
  • the structures for BINAP, BIPHEMP and MeO-BIPHEP are illustrated as below.
  • the present invention provides a compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, which is a new chiral biphenyl diphosphine ligand:
  • R 1 , R 2 , and R 3 are independently H, alkyl or aryl;
  • R 6 and R 7 are independently a substituent
  • A is independently aryl or heteroaryl, optionally substituted by one or more substituents.
  • the present invention also provides a new intermediate and a process for the preparation of the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, of the present invention.
  • the present invention further provides a chiral transition metal catalyst containing: the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, of the present invention; and a transition metal, or an ion or a complex thereof.
  • the present invention additionally provides use of the chiral transition metal catalyst of the present invention in asymmetric reactions.
  • alkyl refers to unsubstituted or substituted straight- or branched-chain hydrocarbon groups having 1-20 carbon atoms, preferably 1-7 carbon atoms.
  • exemplary unsubstituted alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl and the like.
  • Substituted alkyl groups include, but are not limited to, alkyl groups substituted by one or more of the following groups: halo, cycloalkyl, alkoxy or aryl.
  • aryl refers to a phenyl group, which may optionally be substituted by 1-4 substituents, such as optionally substituted alkyl, cycloalkyl, halo or alkoxy.
  • heteroaryl refers to a monocyclic, bicyclic or tricyclic ring system containing one or two aromatic rings and from 5 to 14 atoms of which, unless otherwise specified, one, two, three, four or five are heteroatoms independently selected from N, 0 and S and includes thienyl, furyl, pyrrolyl, pyridyl, indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like.
  • the heteroaryl is furyl or pyridyl.
  • cycloalkyi refers to optionally substituted monocyclic aliphatic hydrocarbon groups of 3-6 carbon atoms, which may be substituted by one or more substituents, such as alkyl, alkoxy or halo.
  • alkoxy refers to alkyl-O-.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • substituted(s) refers to alkyl, cycloalkyi, alkoxy or halo.
  • the present invention provides a compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof:
  • R 1 , R 2 , and R 3 are independently H, alkyl or aryl;
  • R 6 and R 7 are independently a substituent
  • A is independently aryl or heteroaryl, optionally substituted by one or more substituents.
  • R 1 , R 2 , R 3 , R 6 and R 7 are independently H or alkyl, and more preferably, are independently H.
  • A is phenyl optionally substituted by one or more substituents, and more preferably,
  • the compound of formula (I) is the following compound or mixture thereof:
  • the stereoisomer of the compound of formula (I) includes enantiomers and diastereomers.
  • the stereoisomer of the compound of formula (I) is an isomer of formula (l-la) to (l-ld) or mixture thereof, due to the chiral center in the sidechain and also the axial chirality of the biphenyl system:
  • R 1 , R 2 , R 3 , R 6 , R 7 and A are defined as above.
  • stereoisomer of the compound of formula (I) is the following isomers or mixture thereof:
  • the compounds of the present invention preferably have an optical purity of at least 85% enantiomeric excess (ee) and diastereomer excess (de), more preferably at least 95% ee and de, and most preferably at least 98% ee and de.
  • the present invention provides a new intermediate of formula (II), or a stereoisomer thereof, or a stereoisomeric mixture thereof:
  • R 1 , R 2 , R 3 , R 6 , R 7 and A are defined as above.
  • the stereoisomer of the compound of formula (II) includes enantiomers and diastereomers.
  • the stereoisomer of the compound of formula (II) is an isomer of formula (ll-la) to (II- ld) or mixture thereof, due to the chiral center in the sidechain and also the axial chirality of the biphenyl system:
  • the intermediate of formula (II), or a stereoisomer thereof, or a stereoisomeric mixture thereof may be used for the preparation of the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, according to the method disclosed herein.
  • the present invention provides a process for the preparation of the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, comprising:
  • R 1 , R 2 , R 3 , R 6 , R 7 and A are defined as above.
  • the compound of formula (II) is reduced with a reducing agent, such as trichlorosilane, in a solvent, such as xylene, toluene and tetrahydrofuran (TH F), in the presence of a base, such as trimethylamine and tributylamine, to provide the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof.
  • a reducing agent such as trichlorosilane
  • a solvent such as xylene, toluene and tetrahydrofuran (TH F)
  • a base such as trimethylamine and tributylamine
  • the reducing agent may be added in an amount of from 2 moles to 20 moles, preferably from 2 moles to 10 moles, more preferably from 4 moles to 8 moles, per mole of the compound of formula (II), or a stereoisomer thereof, or a stereoisomeric mixture thereof;
  • the base may be added in a n a mount of from 2 moles to 20 moles, preferably from 2 moles to 10 moles, more preferably from 4 moles to 8 moles, per mole of the compound of formula (II), or a stereoisomer thereof, or a stereoisomeric mixture thereof.
  • the reaction may be carried out under the temperature of from 50 °C to 200 °C, preferably from 100 °C to 160 °C, more preferably under reflux.
  • the reaction may be carried out under the protection of inert gases, such as nitrogen or argon .
  • the product of the process i.e., the compound of the formula (I), or a stereoisomer thereof, or a stereoisomeric mixtu re thereof, may be easily purified from the reaction mixture, for example, by extraction, recrystallization and column chromatography for the further application.
  • the intermediate of formula (II), or a stereoisomer thereof, or a stereoisomeric mixture thereof may be produced by a process comprising:
  • R 1 , R 2 , R 3 , R 6 and R 7 are defined as above, and R 8 is alkyl and X is halogen.
  • the solvent may be added in an amount of from 500 mL to 2000 mL, preferably from 800 mL to 1500 mL, more preferable from 1000 mL to 1200 mL, per mole of the compound of formula (III); and the base may be added in an amount of from 2 moles to 10 moles, preferably from 2 moles to 5 moles, per mole of the compound of formula (III).
  • the reaction may be carried out under the protection of inert gas such as nitrogen, the temperature of the reaction may be from 20 °C to 150 °C, preferably under reflux.
  • the obtained compound of formula (lll-l) may be isolated from the reaction of the step 1) by any known process such as extraction for the next step.
  • the conversion may be achieved by a Grignard reaction and a coupling reaction.
  • the conversion includes a Grignard reaction followed by a coupling reaction as indicated below.
  • the conversion includes a coupling reaction followed by a Grignard reaction as indicated below.
  • a chlorination reagent such as SOCI 2 may be added at first for chlorination reaction in a solvent, such as THF, in the presence of a catalyst, such as dimethylformamide (DMF), and then a Grignard reagent (A-MgX, A and X are defined as above) are added for Grignard reaction in a solvent, such as THF.
  • a catalyst such as dimethylformamide (DMF)
  • a Grignard reagent A-MgX, A and X are defined as above
  • a coupling reagent such as lithium diisopropylamide (LDA) or Lithium 2,2,6,6-tetramethylpiperidide (LiTMP) may be added for reaction in a solvent, such as THF or diethyl ether (Et20), in the presence of an oxidant, such as FeCb.
  • LDA lithium diisopropylamide
  • LiTMP Lithium 2,2,6,6-tetramethylpiperidide
  • Et20 diethyl ether
  • the conversion is carried out under an inert atmosphere, for example, under the protection of nitrogen or argon.
  • the compound of formula (III) may be produced by a process comprising: a) reacting the compound of formula (IV) with the compound of formula (V) to obtain a compound of formula (VI);
  • R 1 , R 2 , R 3 , R 6 , R 7 and X are defined as above;
  • R 4 is H, alkyl or aryl; and
  • R 5 is H.
  • the reaction may be ca rried out under Mitsunobu reaction conditions, for example, in a solvent, such as TH F or Et 2 0, in the presence of phosphine, such as triphenylphosphine (PPh 3 ), and an azo compound, such as diethyl azodicarboxylate (DEAD), diisopropyl azodicarboxylate (DIAD) and l,l'-(azodicarbonyl)dipiperidine (ADDP).
  • a solvent such as TH F or Et 2
  • phosphine such as triphenylphosphine (PPh 3 )
  • an azo compound such as diethyl azodicarboxylate (DEAD), diisopropyl azodicarboxylate (DIAD) and l,l'-(azodicarbonyl)dipiperidine (ADDP).
  • DEAD diethyl azodicarboxylate
  • DIAD diisopropyl azodicarboxy
  • the compound of formula (V) may be added in an amount of from 1 mole to 10 moles, preferably from 1 mole to 4 moles, more preferably from 1 mole to 2 moles, per mole of the compound of formula (IV); and the phosphine may be added in an amount of from 1 mole to 10 moles, preferably from 1 mole to 4 moles, more preferably from 1 mole to 2 moles, per mole of the compound of formula (IV).
  • the reaction of the step a) of the process may be carried out at the temperatu re of from 0 °C to 100 °C, preferably from 20 °C to 60 °C.
  • the resulted product from the step a) may be used for the next step after filtration and concentration.
  • the compound of formula (IV) and the compound of formu la (V) are commercially available or synthesized by a method known in the art (see Carla S.M. Pereira ef. al., Chemical Engineering Science, Volume 64, Issue 14, 15 July 2009, Pages 3301-3310).
  • the reduction may be carried out in the way of ester reduction methods known in the art (see Svenja Maschinenmeister ef. al., Org. Process Res. Dev., 2014, 18(2), pp 289-302).
  • the used reducing agent is selected from Na BH 4 and LiAI H 4 , and the reducing agent is added in an amount of from 1 mole to 10 moles, preferably from 2 moles to 8 moles, preferably from 4 moles to 6 moles, per mole of the compound of formula (VI- 1).
  • CaCI 2 , MgCI 2 or ZnCI 2 is preferably added in an amount of from 2 moles to 4 moles, per mole of the compound of the formula (VI-1).
  • the reaction of the step b) of the process may be carried out at the temperature of from -10 °C to 100 °C, preferably from 0 °C to 40 °C.
  • the resulted product of the compound of formula (VI-1) may be used for the next step after extraction and concentration.
  • step c) of the process the reaction may be carried out under Mitsunobu reaction conditions same as step a).
  • the resulted product of the compound of formula (III) may be used for the next step with or without purification.
  • the compound of formula (II) may be produced from the compound of formula (VI- 1) by a nucleophilic substitution reaction.
  • the nucleophilic substitution reaction includes the following steps:
  • Step (c-1) converting the compound of formula (VI-1) into a compound of the formula (VI-2) by adding a leaving group:
  • Step (c-2) reacting the compound of formula (VI-2) with the compound of formula (V-1) to produce the compound of formula (III).
  • R 1 , R 2 , R 3 , R 6 , R 7 and X are defined as above and Y is a leaving group such as toluenesulfonic (Ts) group or methanesulfonic (Ms) group.
  • the reaction may be carried out in the presence of a base, such as Et 3 N, and a chloride of the leaving group, such as p-toluenesulfonyl chloride or methanesulfonyl chloride.
  • a base such as Et 3 N
  • a chloride of the leaving group such as p-toluenesulfonyl chloride or methanesulfonyl chloride.
  • the reaction may be carried out in a solvent, such as d imethyl su lphoxide (DMSO), dimethylformamide (DMF), CH 3 CN and acetone, in the presence of a base, such as K 2 C0 3 , Cs 2 C0 3 and Na 2 C0 3 .
  • the present invention provides a chiral transition metal catalyst that contains: a compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof; and a transition metal, or an ion or a complex thereof:
  • R 1 , R 2 , R 3 , R 6 , R 7 a nd A are defined as above.
  • the transition metal may be iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, and is especially ruthenium, rhodium or iridium.
  • the chiral transition metal cata lyst of the present application contains the metal of rutheniu m, rhod iu m or iridium, and 1 mole to 5 moles, preferably 1 moles to 2 moles of the compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, per mole of the metal.
  • the chiral transition meta l cata lyst of the present application may be obtained by reacting a compound of formula (I), or a stereoisomer thereof, or a stereoisomeric mixture thereof, with a suitable metal salt, or a suitable metal complex of a transition metal.
  • the chiral transition metal catalyst may be generated in situ, or it may be isolated prior to use.
  • the ch iral transition metal catalyst of the present invention obta inable as described herein may be employed for converting a prochiral substrate to a ch iral product under reaction conditions otherwise suitable for asymmetric induction. Accordingly, in the fifth aspect, the present invention provides a method for converting a prochiral substrate to a chiral product by using the chiral transition metal cata lyst of the present invention in asymmetric reactions.
  • Such asymmetric reactions include, but are not limited to, catalytic hydrogenation, hydrosilylation, hydroboration, hydroformylation, hydrocarboxylation, hyd roacylation, Heck reaction and some allylic isomerization and substitution reactions.
  • a preferred reaction for asymmetric induction using a chiral transition metal cata lyst of the present application is catalytic hydrogenation.
  • the chiral transition metal cata lysts of the present invention are especially effective when employed in asymmetric catalytic hydrogenation of cyclic anhydride (CAN) into L-Lactone (LAP) as shown below:
  • Step IV tetraethyl (((2R)-propane-l,2-diylbis(oxy))bis(3,l-phenylene))bis(phosphonate)
  • Step V (((2R)-propan-l,2-diylbis(oxy))bis(3,l-phenylene))bis(bis(3,5-ditertbutyl-4- methoxyphenyl)phosphine oxide)
  • Example 9 Asymmetric hydrogenation of CAN to LAP

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un nouveau ligand de diphosphine de biphényle chiral de formule (I), dans laquelle R1, R2 et R3 représentent indépendamment H, alkyle ou aryle ; R6 et R7 sont indépendamment un substituant ; et A est indépendamment un aryle ou hétéroaryle, éventuellement substitué par un ou plusieurs substituants, ou un stéréoisomère de ceux-ci, ou un mélange stéréoisomérique de ceux-ci.
PCT/EP2018/059021 2017-04-11 2018-04-09 Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation Ceased WO2018189107A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201880023975.2A CN110494439B (zh) 2017-04-11 2018-04-09 手性联苯二膦配体及其制备方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2017080063 2017-04-11
CNPCT/CN2017/080063 2017-04-11

Publications (1)

Publication Number Publication Date
WO2018189107A1 true WO2018189107A1 (fr) 2018-10-18

Family

ID=61913181

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/059021 Ceased WO2018189107A1 (fr) 2017-04-11 2018-04-09 Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation

Country Status (2)

Country Link
CN (1) CN110494439B (fr)
WO (1) WO2018189107A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020234526A1 (fr) 2019-05-17 2020-11-26 Safran Helicopter Engines Dispositif et procédé de fabrication additive par fusion laser sur lit de poudre

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111205208B (zh) * 2020-01-16 2021-12-17 郑州恒诚仪器耗材有限公司 环己烷-1,3-二酮类化合物及其合成方法和应用
WO2021143617A1 (fr) * 2020-01-16 2021-07-22 郑州手性药物研究院有限公司 Composé d'éther d'oxime cyclohexadiène, son procédé de synthèse et son utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016536A1 (fr) 1991-03-15 1992-10-01 F. Hoffmann-La Roche Ag Phosphines chirales
US5302738A (en) 1991-03-15 1994-04-12 Hoffmann-La Roche Inc. Chiral phosphines
EP0667350A1 (fr) 1994-02-12 1995-08-16 F. Hoffmann-La Roche Ag Dérivés de phosphines solubles dans l'eau
US20050014633A1 (en) * 2003-07-11 2005-01-20 Chan Albert Sun-Chi Biphenyldiphosphine compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111063A2 (fr) * 2003-06-13 2004-12-23 Lanxess Deutschland Gmbh Ligands chiraux a utiliser dans des syntheses asymetriques
DE102004022898A1 (de) * 2004-05-10 2005-12-08 Bayer Chemicals Ag Chirale Diphosphinoterpene und deren Übergangsmetallkomplexe
DE102004052040A1 (de) * 2004-10-26 2006-04-27 Basf Ag Liganden zur asymmetrischen Hydroformylierung
CN101230075A (zh) * 2008-02-22 2008-07-30 武汉大学 中心手性诱导的轴手性双膦配体及其合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016536A1 (fr) 1991-03-15 1992-10-01 F. Hoffmann-La Roche Ag Phosphines chirales
US5302738A (en) 1991-03-15 1994-04-12 Hoffmann-La Roche Inc. Chiral phosphines
EP0667350A1 (fr) 1994-02-12 1995-08-16 F. Hoffmann-La Roche Ag Dérivés de phosphines solubles dans l'eau
US20050014633A1 (en) * 2003-07-11 2005-01-20 Chan Albert Sun-Chi Biphenyldiphosphine compounds

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CARLA S.M. PEREIRA, CHEMICAL ENGINEERING SCIENCE, vol. 64, no. 14, 15 July 2009 (2009-07-15), pages 3301 - 3310
DAMIEN HERAULT, CHEM. SOC. REV., vol. 44, 2015, pages 2508 - 2528
NOYORI; TAKAYA, ACC. CHERN. RES., vol. 23, 1990, pages 345
OLKUMA ET AL., AM. CHERN. SOC., vol. 120, 1998, pages 13529
SCHMID ET AL., PURE &APPL. CHERN., vol. 68, 1996, pages 131
SVENJA WERKMEISTER, ORG. PROCESS RES. DEV., vol. 18, no. 2, 2014, pages 289 - 302

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020234526A1 (fr) 2019-05-17 2020-11-26 Safran Helicopter Engines Dispositif et procédé de fabrication additive par fusion laser sur lit de poudre

Also Published As

Publication number Publication date
CN110494439B (zh) 2022-11-08
CN110494439A (zh) 2019-11-22

Similar Documents

Publication Publication Date Title
US6037500A (en) Asymmetric synthesis catalyzed by transition metal complexes with cyclic chiral phosphine ligands
Berthod et al. 4, 4′ and 5, 5′-DiamBINAP as a hydrosoluble chiral ligand: syntheses and use in Ru (II) asymmetric biphasic catalytic hydrogenation
JP5685071B2 (ja) 新規ルテニウム錯体及びこれを触媒とする光学活性アルコール化合物の製造方法
KR100384411B1 (ko) 키랄리간드인헤테로방향족디포스핀
Berthod et al. New perfluoroalkylated BINAP usable as a ligand in homogeneous and supercritical carbon dioxide asymmetric hydrogenation
JP2010070510A (ja) ルテニウム錯体の製造方法
WO2018189107A1 (fr) Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation
WO2005117907A2 (fr) Phospholanes p-chiraux et composes phosphocycliques, et leur utilisation dans des reactions catalytiques asymetriques
Yuan et al. Zinc (II)‐Catalyzed Mannich‐type Reactions of Hydrazones with Difluoroenoxysilane and Its Application in the Synthesis of Optically Active 2, 2‐Difluoro‐3‐oxo‐benzohydrazide
JP5271503B2 (ja) 有機ホウ素化合物の製造方法
Liu et al. Discovery of chiral catalysts by asymmetric activation for highly enantioselective diethylzinc addition to imines: using racemic and achiral diimines as effective activators
JP2010529048A (ja) アミノホスフィンリガンドを調製するための方法およびその金属触媒における使用
Chien et al. Enantioselective synthesis of 1-vinyltetrahydroisoquinolines via Pd-catalyzed intramolecular asymmetric allylic amination reactions
AU2011301115A1 (en) Biaryl diphosphine ligands, intermediates of the same and their use in asymmetric catalysis
JP4928798B2 (ja) 不斉合成用触媒およびそれに用いる配位子、並びにこれらを用いた不斉合成反応による光学活性化合物の製造方法
Lorraine et al. Biaryl diphosphine ligands and their ruthenium complexes: Preparation and use for catalytic hydrogenation of ketones
JP5283175B2 (ja) 新規ジホスフィン化合物、その製造方法及びそれを含む金属錯体
JPWO2019069828A1 (ja) 光学活性な２，３−ビスホスフィノピラジン誘導体、その製造方法、遷移金属錯体及び有機ホウ素化合物の製造方法
JP2008169201A (ja) 新規光学活性ビアリールリン化合物とその製造方法
Gök et al. A novel C2-symmetric bisphosphane ligand with a chiral cyclopropane backbone: synthesis and application in the Rh (I)-catalyzed asymmetric 1, 4-addition of arylboronic acids
Zhang et al. Synthesis of atropisomeric 5, 5′-linked biphenyl bisaminophosphine ligands and their applications in asymmetric catalysis
Wei et al. Novel atropisomeric bisphosphine ligands with a bridge across the 5, 5′-position of the biphenyl for asymmetric catalysis
JP4226847B2 (ja) ホスフィン−ホスホラン化合物と遷移金属とを含有する遷移金属錯体の存在下、α，β−不飽和アミド誘導体から光学活性アミド類を製造する方法。
Jiang et al. Pd (II)-catalyzed and diethylzinc-mediated asymmetric umpolung allylation of aldehydes in the presence of chiral phosphine-Schiff base type ligands
Liu et al. Convenient synthesis of tropos phosphine-oxazoline ligands

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18716610

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18716610

Country of ref document: EP

Kind code of ref document: A1