Methods for formation of aryl-sulfur and aryl-selenium compounds using copper(I) catalysts
A mild, palladium-free synthetic protocol for the cross-coupling reaction of vinyl or aryl iodides and thiols or selenols using, in certain embodiments, 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 ° C. A variety of vinyl/aryl sulfides and vinyl/aryl selenides can be synthesized in excellent yields from readily available iodides and thiols or selenols.
1. A method of using a Cu(I) compound for aryl-sulfur and aryl-selenide bond formation, said method comprising:
providing an aryl halide, and one of a thiol and a selenol; and
contacting said halide and one of said thiol and said selenol with a Cu(I) compound selected from a Cu(I) salt, a bi-dentate ligand, and the reaction product of said Cu(I) salt and said bi-dentate ligand.
2. The method of claim 1 wherein said Cu(I) compound is in an amount less than stoichiometric.
3. The method of claim 2 wherein said bi-dentate ligand is selected from 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline.
4. The method of claim 3 wherein said Cu(I) compound comprises a Cu(I) halide and one of said bi-dentate ligands.
5. The method of claim 1 further comprising a base component.
6. The method of claim 1 wherein said thiol is selected from aryl and alkyl thiols, and said selenol is selected from aryl and alkyl selenols.
7. A system for aryl-sulfur and aryl-selenide bond formation, said system comprising:
an aryl halide;
a compound selected from a thiol, said thiol selected from aryl and alkyl thiols, and a selenol, said selenol selected from aryl and alkyl selenols; and
a Cu(I) compound selected from a Cu(I) salt, a bi-dentate ligand, and a reaction product of said Cu(I) salt and said bi-dentate ligand, said Cu(I) compound present in an amount less than stoichiometric.
8. The system of claim 7 comprising a catalytic amount of said Cu(I) compound.
9. The system of claim 7 wherein said bi-dentate ligand is selected from 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline.
10. The system of claim 9 wherein said Cu(I) compound comprises a chelation product of a Cu(I) halide and one of said bi-dentate ligands.
11. The system of claim 7 further comprising a solvent.
12. The system of claim 7 further comprising a base component.
13. A method for coupling halides and thiols, said method comprising:
providing an enyl halide compound, said enyl halide compound selected from aryl halides and vinyl halides;
providing a thiol compound, said thiol compound selected from alkyl thiols, aryl thiols and heterocyclic thiols; and
contacting said halide and thiol compounds with a medium comprising a Cu(I) compound selected from a Cu(I) salt, a bi-dentate ligand, and a reaction product of said Cu(I) salt and said bi-dentate ligand, said Cu(I) compound in an amount less than stoichiometric, and said medium further comprising a solvent component.
14. The method of claim 13 wherein said enyl halide is a vinyl halide selected from cyclic and acyclic vinyl iodides.
15. The method of claim 13 wherein said thiol is a thiophenol.
16. The method of claim 13 wherein said bi-dentate ligand is selected from 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline.
17. The method of claim 16 wherein said Cu(I) compound is selected from Cu(phen)(PPh 3 ) 2 NO 3 and CuI/neocuproine.
18. The method of claim 17 wherein said solvent is selected from toluene and isopropyl alcohol.
19. The method of claim 18 wherein said medium further comprises a base component.
20. The method of claim 19 wherein said base component is K 3 PO 4 .