Oxidative homo-coupling reactions of aryl boronic acids using a porous copper metal-organic framework as a highly efficient heterogeneous catalyst
The disclosure provides methods for the use of open metal frameworks to catalyze coupling reactions.
1. A method to connect aryls by homocoupling comprising contacting a porous metal organic framework (MOF) or a porous metal organic polyhedral (MOP) with boronic acid substituted aryls wherein the MOF or MOP catalyze the synthesis of a biaryl through a homo-coupling reaction, wherein the MOF or MOP comprises a plurality of linking moieties that have a substructure selected from the group consisting of (C 1 -C 20 )alkyl, (C 3 C 20 )cycloalky, aryl, (C 1 -C 20 )alkylamine, arylamine, and heterocycle; and wherein the substructure has one or more covalently attached CO 2 H linking clusters that undergo condensation with a copper metal and wherein the MOF or the MOP comprise open copper centers that are mono-dispersed throughout the pores.
2. The method of claim 1 , wherein the method further comprises cupric acetate.
3. The method of claim 1 , wherein the method further comprises a solvent.
4. The method of claim 1 , wherein the method further comprises a base.
5. The method of claim 4 , wherein the copper center of the MOF or the MOP forms a coordinate bond with the base.
6. The method of claim 1 , wherein the method further comprises an oxidant.
7. The method of claim 6 , wherein the one or more oxidant is air.
8. The method of claim 1 , wherein the method is performed at room temperature.
9. The method of claim 1 , wherein the boronic acid substituted aryls are phenylboronic acids that can be optionally substituted at the para position.
10. The method of claim 9 , wherein the boronic acid substituted aryls comprise the general structure of:
wherein,
R is selected from the group consisting of H, nitro, cyano, Cl, t-Bu, and N(CH 3 ) 2 .
11. The method of claim 1 , wherein the boronic acid substituted aryls is boronic acid substituted naphthalene that may or may not be further substituted.
12. The method of claim 11 , wherein the boronic acid substituted naphthalene is 1-naphthylboronic acid.
13. The method of claim 1 , wherein the MOF or MOP comprises one or more linking moieties comprising:
wherein,
R 1 -R 15 are independently selected from the group consisting of H, NH 2 , CN, OH, SH, P, Br, Cl, I, F,
and
X is either 1, 2, or 3.
14. The method of claim 13 , wherein the MOF or MOP comprises one or more linking moieties comprising:
wherein,
R 1 -R 3 are independently selected from the group consisting of H, NH 2 , CN, OH, SH, P, Br, Cl, I, F,
and X is either 1, 2, or 3.
15. The method of claim 14 , wherein the MOF or MOP comprises one or more linking moieties comprising:
16. The method of claim 1 , wherein the MOF or MOP contains a transition metal.
17. The method of claim 16 , wherein the MOF or MOP contains Cu.
18. A method to connect aryls by homocoupling comprising contacting a metal organic framework (MOF) with boronic acid substituted aryls, wherein the MOF catalyzes the synthesis of a biaryl through a homo-coupling reaction, and wherein the MOF comprises Cu 3 (BTC) 2 (where BTC is benzene-1,3,5-tricarboxylate).
19. The method of claim 1 , wherein the method can be repeated for one or more cycles with the same MOF or MOP.