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WO1998005671A1 - Composes organosilicies et leur utilisation en chimie combinatoire - Google Patents

Composes organosilicies et leur utilisation en chimie combinatoire Download PDF

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Publication number
WO1998005671A1
WO1998005671A1 PCT/GB1997/002128 GB9702128W WO9805671A1 WO 1998005671 A1 WO1998005671 A1 WO 1998005671A1 GB 9702128 W GB9702128 W GB 9702128W WO 9805671 A1 WO9805671 A1 WO 9805671A1
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compounds
support
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compound
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PCT/GB1997/002128
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English (en)
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Neal David Hone
Anthony David Baxter
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Oxford Asymmetry International Plc.
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Publication of WO1998005671A1 publication Critical patent/WO1998005671A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B80/00—Linkers or spacers specially adapted for combinatorial chemistry or libraries, e.g. traceless linkers or safety-catch linkers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B50/00—Methods of creating libraries, e.g. combinatorial synthesis
    • C40B50/14—Solid phase synthesis, i.e. wherein one or more library building blocks are bound to a solid support during library creation; Particular methods of cleavage from the solid support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the invention relates to a method for preparing compounds comprising at least one carbon atom in an aromatic ring.
  • This invention also relates to improved silane linkers, to methods for their preparation and to their use in the synthesis of such compounds and of compound libraries.
  • Such libraries may be screened as pharmaceutical agents .
  • Combinatorial chemistry may involve the reaction of each member of one pool of X number of preferably commercially available reagents (e.g. amines) with each of Y members of another pool (e.g. acid chlorides) to produce a library of X x Y number of compounds (e.g. amides) . Each member of the X x Y products could then be reacted with a further pool of Z number of compounds to give a total of X x Y x Z compounds and so on.
  • X number of preferably commercially available reagents e.g. amines
  • Y members of another pool e.g. acid chlorides
  • a library may comprise a collection of compounds based on a particular core structure. For example, if a core structure such as an aromatic ring can have three independently variable substituents A, B and C then all the possible combinations of A, B and C on the core structure would be present within a library. If substituent A could be any one of a chemical moieties, substituent B any one of b chemical moieties and substituent C any one of c chemical moieties, the total number of compounds in the library would be a x Jb x c.
  • Combinatorial libraries have been prepared using both 'in solution' methods and by solid phase synthesis. Multiple simultaneous solution reactions have successfully yielded useful numbers of a variety of novel compounds for biological screening. However, the need to avoid purification of products in order to make this process viable limits this approach to the use of efficient one or, at the most, two step reactions.
  • Solid phase synthesis on the other hand allows the use of excess reagents to drive reactions to completion, and the facile removal of excess reagents and by-products through simple washing procedures. This provides the possibility of synthesising more complex and diverse structures and lends itself well to automation. Solid phase chemistry therefore offers a more attractive approach to the generation of combinatorial libraries .
  • WO 95/16712 discloses the use of silane linkers in the resin-bound synthesis of substituted aromatic carbocycles and heterocycles .
  • the aromatic compounds are bound to the resin support through a silane linker comprising the moiety
  • D is a Ci-Cjo alkyl chain optionally having one or more intervening heteroatoms or aryl groups ;
  • R' ' and R' ' ' are independently C ⁇ to C 6 alkyl.
  • a plurality of resin-bound aromatic compounds are derivatised to give a library of compounds .
  • Such compounds may then be cleaved from the silane linker by protodesilylation with a strong protic acid, such as HF or 100% trifluoroacetic acid.
  • a strong protic acid such as HF or 100% trifluoroacetic acid.
  • Various other electrophiles are also disclosed which bring about cleavage from the linker.
  • the cleavage reactions are lengthy and employ harsh reaction conditions, which may be incompatible with some functional groups present in a diverse library set.
  • a silane linker for use in the solid state synthesis of biphenyl derivatives is disclosed in Han et al, Tetrahedron Letters, ,12, 2703-2706, 1996. Cleavage of the biphenyl derivatives from the silane linker is brought about by treatment with trifluoroacetic acid or an electrophile . However, the yields of the cleavage reactions are variable and are dependent on the nature of the substituents on the phenyl rings.
  • the release of combinatorial compound libraries from a resin support ideally provides quantitative cleavage, or at least equimolar cleavage, of each component to allow viable comparisons to be made of biological data from arrays of compounds synthesised in insufficient quantity for accurate weight determination.
  • the cleavage reactions must therefore be efficient and predictable in order for the silane linkers to be useful as combinatorial tools.
  • the linkers must themselves be stable to the cleavage conditions to avoid the possibility of product contamination through linker degradation.
  • Liquid hydrofluoric acid is known to effect aryl-silicon cleavage.
  • HF Liquid hydrofluoric acid
  • R 1 and R 2 independently of one another, denote C ! -C 10 alkyl, cycloalkyl or aralkyl;
  • R 3 and R 4 independently of one another, denote hydrogen, alkyl, cycloalkyl or aralkyl
  • n denotes 1 or 2 ;
  • n denotes 1
  • X denotes 0, S, NR 3 , OC(R 3 R 4 ),
  • n denotes 2
  • X denotes CR 3 R 4 ;
  • R denotes a group comprising at least one aromatic ring which is attached to the silicon atom via a covalent bond from an aromatic carbon atom;
  • A denotes C0 2 R 5 , CONR 5 R 6 , COSR 5 or CSNR 5 R 6 ;
  • R 5 and R 6 independently of one another, denote H, Ci-Cio alkyl, cycloalkyl or aralkyl.
  • the present invention thus provides compounds which are suitable as improved silane linkers for use in producing compounds comprising at least one carbon atom in an aromatic ring.
  • the aromatic ring is attached via a bond from an aromatic carbon atom to a silicon atom to give the compounds of general formula (I) .
  • the compounds of general formula (I) may be present in solution or may be tethered to a support via the group A. Synthetic chemistry is carried out to functionali ⁇ e and/or derivatise the R group. Once the chemistry has been completed, the desired products are released from the linker by cleavage of the aromatic carbon-silicon bond.
  • support-bound compounds for use as silane linkers in chemical synthesis, said support-bound compounds being of general formula (II)
  • P denotes a support, optionally including a tether, attached to the group Y;
  • R, R 1 , R 2 , R 3 , R 4 , X and n are as hereinbefore defined.
  • Preferred compounds of general formula (I) and support-bound compounds of general formula (II) according to the present invention are those wherein
  • R 1 and R 2 independently denote methyl, ethyl, propyl or benzyl ;
  • R 3 and R 4 independently denote hydrogen, methyl, ethyl, propyl or benzyl
  • n denotes l
  • X denotes CR 3 R 4 .
  • Especially preferred compounds of general formula (I) and support-bound compounds of general formula (II) are those wherein
  • R 1 and R 2 both denote methyl
  • R 3 and R 4 both denote hydrogen or both denote methyl
  • n denotes 1;
  • X denotes CH 2 .
  • Preferred compounds of general formula (I) are those wherein A denotes C0R 5 or CONR 5 R 6 , especially CONHBn.
  • Preferred support-bound compounds of general formula (II) are those wherein Y denotes CONR 3 , especially CONH or CONMe.
  • the aromatic carbon atom attached to the silicon atom of the linker may be part of an optionally substituted aryl or heteroaryl ring or ring system which may include bi- or tri-cyclic ring systems.
  • the rings may contain one or more heteroatoms selected from sulphur, oxygen and nitrogen.
  • Examples include, but are not limited to, optionally substituted phenyl, naphthyl, pyridyl, thiophenyl, bi-phenyl, quinolinyl, thiazinyl, isoquinolinyl, imidazolyl, furanyl, pyrrolidinyl, fluorenyl, indolyl or indanyl .
  • Examples of possible substituents of the aromatic ring or ring system include, but are not limited to, alkyl, cycloalkyl, aryl, carboxyl, carboxylic ester, amide, CHO, F, Cl, Br, I, SH, CN, N0 2 , R 3 Sn (wherein R 7 denotes Cj-Cg alkyl, cycloalkyl or benzyl), NR 8 R 9 (wherein R 8 and R 9 , independently of one another, denote H, C ⁇ Ce alkyl, cycloalkyl or benzyl) or OR 10 (wherein R 10 denotes H, C ⁇ -C 6 alkyl, cycloalkyl, phenyl or benzyl) .
  • the Y group is linked covalently, optionally via a tether, to ⁇ a support, which may be an insoluble support.
  • a support which may be an insoluble support.
  • Compounds of general formula (I) wherein A is C0 2 H may, for example, be attached to a support or tether via formation of an amide bond with an amino group on said support or tether, to give compounds of general formula (II) .
  • supports include polystyrene-divinyl benzene co-polymer (Merrifield Resin) , polyamide, aminomethylated polystyrene resin, aminomethylated Tentagel resin, polyamide-kieselguhr composites, polyhipe, cotton, paper and the like.
  • alkyl denotes a straight or branched chain alkyl group and cycloalkyl denotes a cyclic 4, 5 or 6 membered alkane ring.
  • the compounds may be synthesised in solution and then in a final step attached to a support, for example by formation of an amide bond to give compounds of general formula (II) .
  • the following scheme exemplifies this general approach.
  • Any functional groups present in R may be protected if necessary using conventional protecting groups.
  • R a denotes R as hereinbefore defined, or
  • R a denotes SnR u R 12 R 13 wherein R 11 , R 12 and R 13 , independently of one another, denote -Ce alkyl, cycloalkyl or benzyl,
  • R 1 , R 2 , R 3 , R 4 , X, A and n are as hereinbefore defined,
  • R is as hereinbefore defined and Hal denotes bromine or iodine.
  • the introduction of the group R may be final step in the synthesis of compounds of general formula (I) or (II) , for example by displacement of a tin atom attached to the silicon.
  • the following scheme illustrates this general approach. rhffltip 2
  • R 11 , R 1 and R 13 are as hereinbefore defined.
  • R 1 , R 2 , R 3 , R 4 , X, A, n, R 11 , R 12 and R 13 are as hereinbefore defined,
  • R is as hereinbefore defined and Hal denotes bromine or iodine.
  • support-bound compounds of general formula (II) Similar methodology may also be used to prepare support-bound compounds of general formula (II) .
  • the invention therefore also provides a process for the preparation of support-bound compounds of general formula (II) which comprises reacting a compound of general formula (V)
  • R 1 , R 2 , R 3 , R 4 , X, Y, P, n, R n , R 12 and R 13 are as hereinbefore defined,
  • R is as hereinbefore defined and Hal denotes bromine or iodine.
  • Chemistry may be carried out on the compounds of general formula (I) in solution, for example in dichloromethane .
  • the rapid cleavage of the R-Si bond in the compounds of the invention allows the introduction of groups which it would otherwise be difficult to introduce.
  • the compounds of formula (I) may be cleaved to leave compounds which are labelled at the cleavage site, for example with deuterium, tritium or radio-labels such as 125 I.
  • the invention also provides a method for producing a library of compounds.
  • a compound library a plurality of compounds comprising at least one carbon atom in an aromatic ring are attached to individual supports via a silane linker to form bound intermediates of general formula (II) .
  • the silicon atom of the linker is covalently bonded to an aromatic carbon atom in the bound compounds .
  • Additional synthetic chemistry is then carried out on the bound compounds to derivatise and/or functionalise them.
  • the support-bound compounds may optionally be divided into a plurality of portions and each portion subjected to different synthetic chemistry. Different portions may optionally be recombined and further synthetic chemistry performed.
  • the steps of dividing the portions, performing additional synthetic chemistry and recombining the portions may be carried out more than once, using standard techniques .
  • a method of producing a compound library comprising a plurality of compounds comprising at least one carbon atom in an aromatic ring, said method comprising carrying out synthetic chemistry on the R groups of support-bound compounds of general formula (II) to derivatise and/or functionalise them.
  • the method may also include the further step of releasing the R groups as derivatised or functionalised compounds from the support by cleavage of the R-silicon bond.
  • a combinatorial library of 100 compounds may be synthesised from support-bound compounds as shown in Scheme 3.
  • Resin bound biaryl aldehydes may be prepared via four Suzuki and one Stille reaction (R 1 ) .
  • Reductive a ination of each aldehyde with four amines (R 2 ) may provide 20 resin bound secondary amines which may each be capped with 5 electrophiles (R 3 ) .
  • Aryl-silicon bond cleavage with 50% TFA in DCM may then yield each library member as a single compound.
  • Cleavage of the silicon-aromatic carbon bond may be effected by treatment with a strong, preferably protic, acid.
  • Preferred acids include trifluoroacetic acid (TFA) , HCl, H 2 S0 4 , HF, triflie acid, methanesulfonic acid and pyridinium hydrofluoride. It is preferable to use acids which are volatile, and therefore easy to remove once cleavage has occurred.
  • the preferred cleavage conditions are TFA in an organic solvent, for example about 50% TFA in a solvent such as chloroform or dichloromethane .
  • the use of deuterated or tritiated TFA or other protic acids yield the corresponding 2 H or 3 H labelled products respectively.
  • protic acids leaves hydrogen substitution at the carbon atom originally bonded to the silicon atom (protodesilylation) .
  • aromatic carbon-silicon bond cleavage may be effected in the presence of electrophiles to yield substituted aromatic products.
  • electrophiles include Br 2 , Cl 2 , I 2 , acid chlorides, HN0 2 , chloromethyl ethers, acetals and acyl peroxides.
  • the compounds may also be labelled at the cleavage site, for example by using 125 I 2 as the electrophile.
  • treatment of a bound compound with a solution of molecular halogen may yield the corresponding halide directly, via a halodesilylation reaction.
  • a ketone functionality may be introduced by effecting desilylation with an acyl chloride in the presence of a Lewis acid such as A1C1 3 .
  • Nitrodesilylation may be effected by treatment with a solution of nitrous acid.
  • Ether formation may be effected by treatment of the bound compound with a chloromethyl ether or an acetal in the presence of a Lewis acid such as A1C1 3 or TiCl 4 .
  • the bound compound has an electron withdrawing substituent (e.g. Cl or N0 2 ) ortho to the silicon
  • treatment with aldehydes or alkyl halides in the presence of a fluoride ion source e.g. KF, CsF or TBAF
  • a fluoride ion source e.g. KF, CsF or TBAF
  • analogous reactions may be performed through prior activation of the aromatic ring as a chromium tricarbonyl complex.
  • Treatment of the bound compounds with acyl peroxides may yield the acylated products at the original site of attachment to the silicon atom. Hydrolysis of the ester functionality may then yield the resulting hydroxyl derivatives .
  • direct hydroxy-desilylation may be effected by treatment with sulphonyloxaziridines .
  • Aminodesilylation may be effected with an electrophilic nitrogen source (e.g. NH 2 C1) in the presence of fluoride ions. If the aromatic ring has no electron withdrawing substituents, prior activation via chromium tricarbonyl complexation may be required.
  • an electrophilic nitrogen source e.g. NH 2 C1
  • Neat (4) (2.1g) was heated at 150° C for 5 h to yield (5) as a colourless oil which crystallised on trituration (1.6g, 88%) .
  • Aminomethylated polystyrene resin (l mmol N/g) was swelled and washed with N,N-dimethylformamide (DMF) for 15 min. DMF was removed and a solution of 2-(lH- benzotriazole-1-yl) -1, 1, 3, 3-tetramethyluronium tetrafluoroborate (TBTU, 1.284g), hydroxybenzotriazole (HOBt, 306mg) and (5) (1.14g) in DMF added. Diisopropylethylamine (DIEA, 1.38ml) was added to the above suspension with stirring, which was continued at room temperature for 2 h. The resin was washed with DMF, MeOH, dichloromethane (DCM) , MeOH and dried under vacuum to provide functionalised resin (6) . F.vamplp 2
  • the resultant homogenous solution was diluted with water, carefully acidified with 1M citric acid and extracted with ethyl acetate. The organic extracts were washed with water, dried (MgS0) and evaporated to yield (18) as a thin oil which quickly crystallised (70mg, 73%) .
  • Aminomethylated polystyrene resin (1 mmol N/g) was swelled and washed with DMF for 15 min. DMF was removed and a solution of (18) (60mg) , TBTU (52mg) , HOBt (13mg) and DIEA (84 ⁇ l) in DMF added, the suspension then stirred at room temperature for one hour. The resin was washed with DMF, MeOH, DCM, MeOH and dried under vacuum to yield the functionalised resin (19) .
  • a suspension of resin (6) (1 mmol/g) (500mg) in DME was degassed with argon, followed by the addition of naphthalene-1-boronic acid (172mg) , 2M sodium carbonate solution (0.63ml) and tetrakis (triphenylphosphine) palladium (0) (29mg) .
  • the mixture was refluxed for 12 hours under argon, cooled, 25% ammonium acetate added, and stirring continued for 5 min at room temperature.
  • Resin (20) (lOOmg) was treated with trifluoroacetic acid- DCM (1:1, 10ml) , the suspension stirred at room temperature for 2 h. Filtration of the cleavage solution from the resin followed by evaporation yielded the biarylnapthalene (21) (21mg, 100%) .
  • Resin (15) (0.25mmol substitution/g) (800mg) was swelled in DMF for 15 min. DMF was removed, the resin then treated with 1% hydrazine monohydrate in DMF for 30 min at room temperature. The resin was then washed with DMF, MeOH, DCM, MeOH and dried to yield the aniline functionalised resin (22) .
  • the resin (25) (lmmol substitution/g) (50mg) , derived from the Suzuki coupling of 4-tolylboronic acid and resin (6) via the method for the preparation of resin (20) was treated with TFA-DCM (1:1) at room temperature with stirring for 2 h. Filtration of the cleavage solution from the resin followed by evaporation yielded the product (26) (6mg, 71%) .
  • the resin (20) was suspended in a solution of 3% bromine in 85% aqueous acetic acid, the mixture then stirred at room temperature for 12 h. Filtration of the cleavage solution from the resin followed by evaporation yielded the brominated product (27) (17mg, 61%) .
  • the resin (25) (50mg) was washed and swelled in dry 1,2- DCE for 15 min, DCE removed and fresh dry DCE added. Cyclopropanecarbonyl chloride (23 ⁇ l) and aluminium trichloride (7mg) were added, the suspension stirred at room temperature for 5 min. Anhydrous potassium carbonate was then added, stirring then continued overnight. The cleavage solution was filtered off the resin and volatiles removed in vacuo. The solid residue was triturated with dry ether which was filtered and evaporated to yield the ketone (28) (2mg, 18%) .

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Abstract

Cette invention se rapporte à des composés représentés par la formule générale (I) et à des composés, ancrés à un support et représentés par la formule générale (II). Dans ces formules, R, R?1, R2, R3, R4¿, X, A, Y, P et n sont définis dans le descriptif de l'invention. L'invention se rapporte également à l'utilisation de ces composés en chimie combinatoire et pour la synthèse de composés comportant au moins un atome de carbone dans un noyau aromatique.
PCT/GB1997/002128 1996-08-07 1997-08-07 Composes organosilicies et leur utilisation en chimie combinatoire WO1998005671A1 (fr)

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GBGB9616563.4A GB9616563D0 (en) 1996-08-07 1996-08-07 Compounds and methods
GB9616563.4 1996-08-07

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Cited By (4)

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US6147159A (en) * 1998-09-30 2000-11-14 Argonaut Technologies Compositions for organic synthesis on solid phase and methods of using the same
US6416861B1 (en) 1999-02-16 2002-07-09 Northwestern University Organosilicon compounds and uses thereof
US7985882B1 (en) 2002-08-23 2011-07-26 Biotage Ab Compositions for reductive aminations utilizing supported tricarboxyborohydride reagents and methods of using the same
JP2020002121A (ja) * 2018-05-07 2020-01-09 達興材料股▲ふん▼有限公司 シリコン含有化合物、これを用いる液晶組成物および液晶ディスプレイ

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6147159A (en) * 1998-09-30 2000-11-14 Argonaut Technologies Compositions for organic synthesis on solid phase and methods of using the same
US6416861B1 (en) 1999-02-16 2002-07-09 Northwestern University Organosilicon compounds and uses thereof
US7985882B1 (en) 2002-08-23 2011-07-26 Biotage Ab Compositions for reductive aminations utilizing supported tricarboxyborohydride reagents and methods of using the same
JP2020002121A (ja) * 2018-05-07 2020-01-09 達興材料股▲ふん▼有限公司 シリコン含有化合物、これを用いる液晶組成物および液晶ディスプレイ

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