US 12,404,221 B2
Methods of arene alkenylation
Thomas Brent Gunnoe, Palmyra, VA (US); Xiaofan Jia, Hamden, CT (US); and Lucas Isaac Frye, Monmouth Junction, NJ (US)
Assigned to University of Virginia Patent Foundation, Charlottesville, VA (US)
Appl. No. 17/999,273
Filed by University of Virginia Patent Foundation, Charlottesville, VA (US)
PCT Filed May 19, 2021, PCT No. PCT/US2021/033149
§ 371(c)(1), (2) Date Nov. 18, 2022,
PCT Pub. No. WO2021/236764, PCT Pub. Date Nov. 25, 2021.
Claims priority of provisional application 63/027,132, filed on May 19, 2020.
Prior Publication US 2023/0234900 A1, Jul. 27, 2023
This patent is subject to a terminal disclaimer.
Int. Cl. C07C 2/84 (2006.01); B01J 31/22 (2006.01); C07C 17/266 (2006.01); C07C 41/30 (2006.01); C07C 201/12 (2006.01); C07C 253/30 (2006.01); C07D 307/36 (2006.01)
CPC C07C 2/84 (2013.01) [B01J 31/2213 (2013.01); B01J 31/2291 (2013.01); C07C 17/266 (2013.01); C07C 41/30 (2013.01); C07C 201/12 (2013.01); C07C 253/30 (2013.01); C07D 307/36 (2013.01); B01J 2231/4261 (2013.01); B01J 2531/0208 (2013.01); B01J 2531/822 (2013.01); C07C 2523/46 (2013.01)] 24 Claims
 
1. A method of making a substituted arene, comprising:

OG Complex Work Unit Chemistry
wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
a rhodium (I) catalyst having one of the following formula: L2Rh(L′)X, L3RhX, (L1X1)Rh(L′), [(L)2Rh(μ-X)]2, RhX3, [LnRhy(m-X)m], or (L)nRhm
wherein L2 is selected from:
two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
a combination of the neutral first ligand and the neutral bidentate ligand;
wherein L′ is a neutral second ligand coordinated to Rh(I),
wherein X is a mono-anionic group, either coordinated to the metal or not,
wherein L3 is a tridentate first ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L1X1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
wherein y is 1 to 4, m is 1 to 4 and n is 3(m).