TH23977B - Synthesis of ruthenium or osmium metastases. - Google Patents

Abstract

DC60 (09/02/41) This invention relates to the synthesis of a highly reactive, high-yield ruternium-osmium carbine metathesis catalyst from readily available substrates. The catalyst may be in a general form (chemical formula) where: M is ruternium or osmium; X and X1 independently are any anionic ligands; L and L1 are electron-neutralizing ligands; Each R and R to the power of 1 represents a hydrogen or one substituent from the following substituents: C2-C20 alkynyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkynyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkonsulfonyl, and C1-C20 alkonsulfinyl. In addition, the substituent may be replaced by one or two selected substituents from C1-C5 alkyl, halogen, C1-C5 alkoxy, and aryl. When the aryl substituent is phenyl, it may be replaced by another substituent. One or more selected from groups containing halogens, C1-C5 alkyls, or C1-C5 alkoxys, are prototypes. Specific synthesis for vinyl alkylidenes is performed where R is hydrogen and R⁻¹ is -CH₂CR⁻¹² R⁻¹³, and vinyl alkylidenes are also revealed. In addition to simple synthesis (typically one-step synthesis), the reaction can generally be carried out at room temperature or higher, and the resulting products are often used without further post-synthesis purification. This invention relates to the synthesis of a highly reactive, high-yield rusternium and osmium carbine metathesis catalyst from readily available precursors. The catalyst may be in a generic form (chemical formula) where: M is rusternium or osmium; X and X1, independently, are any anionic ligands; L and L1 are electron-neutralizing ligands; Each R and R1 represents a hydrogen or one substituent from the following substituents: C2-C20 alkynyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkynyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkonsulfonyl, and C1-C20 alkonsulfinyl. Additionally, the substituent may be replaced by one or two selected substituents from C1-C5 alkyl, halogen, C1-C5 alkoxy, and aryl. When the aryl substituent is phenyl, it may be replaced by another substituent. One or more selectable groups containing halogens, C1-C5 alkyls, or C1-C5 alkoxys are used as prototypes. Specific synthesis for vinylalkylidenes where R is hydrogen and R1 is -CH₂CR12R13, and vinylalkylidene catalysts are also revealed. In addition to simple synthesis (typically a one-step synthesis), the reaction can generally be carried out at room temperature or higher, and the resulting products are often used without further purification after synthesis.

Claims (23)

1. The method for synthesizing compounds with specific formulas (chemical formulas) consists of the steps of binding the compound with the specified formula (chemical formula), where n is 1 or 2; M is rutternium or osmium; R12 and R13 are independently selected from groups containing hydrogen, substituted substituents, and substituents, where the substituents are selected from groups containing: C1-C18 alkyl, C2-C18 alkynyl, C2-C18 alkynyl, aryl, C1-C18 carboxylate, C1-C18 alkoxy, C2-C18 alkhinyloxy, C2-C18 alkynyloxy, aryloxy, C2-C18 alkoxycarbonil, C1-C18 alkylthio, C1-C18 alkylsulfonyl, and C1-C18 alkylsulfinyl; R17 is chosen from a group consisting of hydrogen, aryl, and C1-C18 alkyls; X and X1 are independent, being any anionic ligands; and L and L1 are independent, being electron-donating neutralizing ligands. 2. Method according to Claim 1, where M is Rutherium. 3. Method according to Claim 1, where R12 and R13 are each independent and selected from a group consisting of hydrogen, unsubstituted C1-C18 alkyls, substituted C1-C18 alkyls, unsubstituted C1-C18 alkenyls, substituted C1-C18 alkenyls, unsubstituted aryls, and substituted aryls. 4. Method according to Claim 1, where substituents R12 and R13 are replaced by a group selected from the group consisting of unreplaced C1-C5 alkyls, replaced C1-C5 alkyls, unreplaced C1-C5 alkoxys, replaced C1-C5 alkoxys, unreplaced eryls, and replaced eryls. 5. Method according to claim 1, where substituents R12 and R13 include functional groups selected from groups comprising hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalxoxy, carbamate, and halogen. 6. Method according to claim 3, where both substituent groups R12 and R13 are phenyl. 7. Method according to claim 3, where R12 and R13 are both methyl. 8. The method according to claim 1, where ligands X and X1 are independent, is selected from groups consisting of hydrogen, halogen, substituted substituents, and unsubstituted substituents, where substituents are selected from groups consisting of C1-C20 alkyl, aryl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldiketonet, aryldiketonet, C1-C20, carboxylate, aryl or C1-C20 alkylsulfonate, C1-C20 alkylthio-C1-C20 alkylsulfonyl, and C1-C20 alkylsulfenyl. 9. Method according to claim 8, where the selected substituent group is from a group containing halogens, C1-C5 alkyl, C1-C5 alkoxy, and phenyl. 10. The method under claim 8, where X and X1 are independent, is selected from a group consisting of chloride, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO,(CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate. 11. Method according to claim 8, where X and X1 are both chlorides. 12. Method according to claim 1, where each L and L1 are phosphine according to the formula PR3R4R5, where R3 is a secondary alkyl or cycloalkyl group and R4 and R5 are independent and selected from groups consisting of aryls, C1-C10 primary alkyls, secondary alkyls and cycloalkyls. 13. The method according to claim 12, where L and L1 are independent, is selected from a group consisting of -P(cyclohexyl)3,-P(cyclopentyl)3, and -P(isopropyl)3. 14. The method for synthesizing compounds according to the given formula (chemical formula) consists of the steps of bonding the given compound (chemical formula) with another given compound (chemical formula), where n is 1 or 2; M is rutternium; R12 and R13 are independently selected from groups containing hydrogen, unsubstituted C1-C18 alkyls, substituted C1-C18 alkyls, unsubstituted C2-C18 alkynyls, substituted C2-C18 alkynyls, unsubstituted aryls, substituted aryls; R17 is selected from groups containing hydrogen, aryls, and C1-C18 alkyls; X and X1 are independently selected from groups containing halogens. CF3CO2,CH3CO2,CFH2CO2, (CH3)3CO,(CF3)2(CH3)CO,(CF3)(CH3)2 CO,PhO,MeO,EtO, tosylate, mesylate, and trifluoromethanesulfonate; and L and L1 were independently selected from groups containing -P(cyclohexyl)3,-P(cyclopentyl)3, and -P(isopropyl)3. 15. Method according to claim 14, where X and X1 are both chlorides and L and L1 are both -P(cyclohexyl)3. 16. Method according to claim 14, where the compound with the formula (chemical formula) is propagyl halide. 17. Method according to claim 14, where the compound with the formula (chemical formula) is a tertiary propagyl halide. 18. Method pursuant to claim 17, where the tertiary propagyl halide is the tertiary propagyl chloride. 19. Method under claim 14 where the binding step occurs in the solvent. 20. The method under claim 19, whereby the solvent is selected from a group consisting of methylene chloride, benzene, and toluene. 21. The method for synthesizing compounds according to the chemical formula (chemical formula) consists of the steps of binding the compound according to the chemical formula (chemical formula) or (chemical formula) with the compound according to the chemical formula (chemical formula), where M is osmium or rutternium; R12 and R13 are independently selected from groups containing hydrogen, substituted substituents, and unsubstituted substituents, where the substituents are selected from groups containing: C2-C18 alkyl, C2-C18 alkynyl, C2-C18 alkynyl, aryl, C1-C18 carboxylate, C1-C18 alkoxy, C2-C18 alkynyloxy, C2-C18 alkynyloxy, aryloxy, C2-C18 alkoxycarbonil, C1-C18 alkylthio, C1-C18 alkylsulfonyl and C1-C18 alkylsulfinyl; R17 is chosen from groups containing hydrogen, aryl, and C1-C18 alkyls; X and X1 are independent of each other and are any anionic ligands; and L and L1 are independent of each other and are chosen from any tertiary phosphine. 22. Method according to claim 21, where; M is rutternium; R12 and R13, each independent of each other, are selected from groups consisting of hydrogen, C1-C18 unsubstituted alkyls, C1-C18 substituted alkyls, C2-C18 unsubstituted alkyls, C2-C18 unsubstituted alkyls, unsubstituted aryls, substituted aryls; R17 is hydrogen; X and X1 are both chlorides; and L and L1, and L2 are triphenylphosphine. 23. The method for synthesizing compounds according to the formula (chemical formula) consists of the steps of binding the compound according to the formula (chemical formula) with a compound according to the formula R17C=CCR12R13R' and then adding a compound according to the formula HX, where n is 1 or 2; M is osmium or ruthenium; R' represents the hydroxyl group. R12 and R13 are independently selected from groups containing hydrogen, replaced substituents, and unreplaced substituents, where the substituents are chosen from the following groups: C1-C18 alkyl, C2-C18 alkynyl, C2-C18 alkynyl, aryl, C1-C18 carboxylate, C1-C18 alkoxy, C2-C18 alkynyloxy, C2-C18 alkynyloxy, aryloxy, C2-C18 alkoxycarbonyl, C1-C18 alkylthio, C1-C18 alkylsulfonyl, and C1-C18 alkylsulfinyl; R17 is selected from groups containing hydrogen, aryl, and C1-C18 alkyl. X and X1 are independently selectable from any anionic ligand, and L and L1 are independently selectable from any electron-neutralizing donor.