	US 11,833,494 B2
	Catalysts and methods for forming alkenyl substituted arenes
Thomas B. Gunnoe, Palmyra, VA (US); Benjamin Austin Vaughan, Dover, NH (US); and Michael S. Webster-Gardiner, Mims, FL (US)
Assigned to University of Virginia Patent Foundation, Charlottesville, VA (US)
Filed by The University of Virginia Patent Foundation, Charlottesville, VA (US)
Filed on Feb. 2, 2023, as Appl. No. 18/163,647.
Application 18/163,647 is a division of application No. 17/188,535, filed on Mar. 1, 2021.
Application 17/188,535 is a continuation of application No. 15/561,212, granted, now 10,967,364, issued on Apr. 6, 2021, previously published as PCT/US2016/023979, filed on Mar. 24, 2016.
Claims priority of provisional application 62/137,853, filed on Mar. 25, 2015.
Prior Publication US 2023/0173476 A1, Jun. 8, 2023
Int. Cl. C07C 2/66 (2006.01); B01J 31/18 (2006.01); B01J 31/22 (2006.01); B01J 31/00 (2006.01); C07C 5/03 (2006.01)

CPC B01J 31/1815 (2013.01) [B01J 31/00 (2013.01); B01J 31/189 (2013.01); B01J 31/2226 (2013.01); B01J 31/2291 (2013.01); C07C 2/66 (2013.01); C07C 5/03 (2013.01); B01J 2231/46 (2013.01); B01J 2531/0244 (2013.01); B01J 2531/822 (2013.01); B01J 2540/22 (2013.01); B01J 2540/225 (2013.01)]

10 Claims

1. A method of making a substituted arene, comprising reacting an arene and olefin with a catalyst and an oxidant, with the proviso that the method is performed in the absence of CO, wherein the catalyst is:

L₂Rh(L′)X;

wherein:

each L is independently a neutral ligand coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor; wherein each L is independently selected from an amine, a pyridine, a phosphine, a phosphite, an ether, a ketone, or an imine;

L′ is a neutral ligand selected from an amine, a pyridine, a phosphine, a phosphite, an ether, a ketone, or an imine;

X is a monoanionic ligand selected from a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, or a carboxylate;

wherein the oxidant is a copper(II) salt, iodate, periodate, nitrogen dioxide, silver salt, peroxide, dioxygen, air, or a combination thereof;

wherein the arene is benzene or naphthalene, wherein the arene is optionally substituted with 1-4 substituents selected from the group consisting of halo, methyl, carboxylate, nitro, and alkoxy;

wherein the olefin is:

and

R is hydrogen, a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, or a heteroaryl;

to form a product, wherein the product is