US 12,466,775 B2
Visible-light mediated organophotoredox catalytic deuteration of aromatic and aliphatic aldehydes
Wei Wang, Tucson, AZ (US)
Assigned to ARIZONA BOARD OF REGENTS ON BEHALF OF THE UNIVERSITY OF ARIZONA, Tucson, AZ (US)
Appl. No. 17/784,537
Filed by ARIZONA BOARD OF REGENTS ON BEHALF OF THE UNIVERSITY OF ARIZONA, Tucson, AZ (US)
PCT Filed Dec. 1, 2020, PCT No. PCT/US2020/062710
§ 371(c)(1), (2) Date Jun. 10, 2022,
PCT Pub. No. WO2021/118827, PCT Pub. Date Jun. 17, 2021.
Claims priority of provisional application 62/946,838, filed on Dec. 11, 2019.
Prior Publication US 2023/0016922 A1, Jan. 19, 2023
Int. Cl. C07B 59/00 (2006.01); C07C 45/61 (2006.01); C07C 47/228 (2006.01); C07C 47/453 (2006.01); C07C 47/542 (2006.01); C07C 47/546 (2006.01); C07C 49/86 (2006.01); C07C 59/74 (2006.01); C07C 255/50 (2006.01); C07D 207/16 (2006.01); C07D 209/42 (2006.01); C07D 213/54 (2006.01); C07D 239/52 (2006.01); C07D 295/155 (2006.01); C07D 295/185 (2006.01); C07D 307/54 (2006.01); C07D 307/83 (2006.01); C07D 333/24 (2006.01); C07D 333/68 (2006.01); C07D 493/04 (2006.01); C07F 7/18 (2006.01); C07J 9/00 (2006.01); C07K 5/065 (2006.01)
CPC C07B 59/00 (2013.01) [C07C 45/61 (2013.01); C07C 47/228 (2013.01); C07C 47/453 (2013.01); C07C 47/542 (2013.01); C07C 47/546 (2013.01); C07C 49/86 (2013.01); C07C 59/74 (2013.01); C07C 255/50 (2013.01); C07D 207/16 (2013.01); C07D 209/42 (2013.01); C07D 213/54 (2013.01); C07D 239/52 (2013.01); C07D 295/155 (2013.01); C07D 295/185 (2013.01); C07D 307/54 (2013.01); C07D 307/83 (2013.01); C07D 333/24 (2013.01); C07D 333/68 (2013.01); C07D 493/04 (2013.01); C07F 7/1804 (2013.01); C07F 7/1892 (2013.01); C07J 9/00 (2013.01); C07K 5/06078 (2013.01); C07B 2200/05 (2013.01)] 15 Claims
 
1. A method for preparing a deuterated aldehyde of formula:
RZ—C(O)-D
wherein:
RZ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocyclyl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl are each optionally substituted with one or more Ra, and RZ is optionally deuterated;
Ra at each occurrence is independently halogen, —CN, —OH, nitro, —O-benzyl, —NH(t-butoxycarbonyl), —NH(benzyloxycarbonyl), or —X—RX, wherein X is bond, O, NH, C(O), OC(O), or C(O)NH; and RX is alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, aryl, heteroaryl, or heterocyclyl, wherein the RX is optionally substituted,
the method comprising:
(i) mixing an aldehyde of formula:
RZ′—C(O)—H
with a photocatalyst and a hydrogen atom transfer agent in a H2O free solvent comprising D2O and an organic solvent under an inert gas to form a mixture;
wherein the photocatalyst is:

OG Complex Work Unit Chemistry
 or a salt thereof;
wherein RZ′ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, or heterocyclyl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl are each optionally substituted with one or more Rb;
Rb at each occurrence is independently halogen, —CN, —OH, nitro, —O-benzyl, —NH(t-butoxycarbonyl), —NH(benzyloxycarbonyl), or —Y—RY, wherein Y is bond, O, NH, C(O), OC(O), or C(O)NH; and RY is alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, aryl, heteroaryl, or heterocyclyl, wherein the RY is optionally substituted, and
(ii) exposing the mixture of (i) to light, thereby producing the deuterated aldehyde.