US 12,281,065 B2
Iron catalyzed highly enantioselective cis-dihydroxylation of quinones
Chi Ming Che, Hong Kong (CN); Tingting Wang, Hong Kong (CN); and Haixu Wang, Hong Kong (CN)
Assigned to Versitech Limited, Hong Kong (CN); and Laboratory for Synthetic Chemistry and Chemical Biology Limited, Hong Kong (CN)
Filed by Versitech Limited, Hong Kong (CN); and Laboratory for Synthetic Chemistry and Chemical Biology Limited, Hong Kong (CN)
Filed on Jan. 17, 2023, as Appl. No. 18/155,431.
Claims priority of provisional application 63/300,198, filed on Jan. 17, 2022.
Prior Publication US 2023/0227393 A1, Jul. 20, 2023
Int. Cl. C07C 50/04 (2006.01); B01J 31/40 (2006.01); C07C 50/12 (2006.01); C07C 50/30 (2006.01); C07C 50/34 (2006.01); C07C 50/36 (2006.01)
CPC C07C 50/04 (2013.01) [B01J 31/4023 (2013.01); C07C 50/12 (2013.01); C07C 50/30 (2013.01); C07C 50/34 (2013.01); C07C 50/36 (2013.01)] 28 Claims
 
1. A method for asymmetric cis-dihydroxylation of a quinone comprising:
(i) maintaining a reaction mixture at a temperature for a period of time sufficient to form a product,
wherein the reaction mixture comprises the quinone, one or more iron-based catalyst(s), and a solvent,
wherein the product comprises a cis-diol,
wherein the one or more iron-based catalyst(s) have the structure of:

OG Complex Work Unit Chemistry
or a stereoisomer thereof,
wherein:
(a) L1 is

OG Complex Work Unit Chemistry
 each occurrence of T′ is an unsubstituted C6 monocyclic group and p is 1;
(b) R18 and R18′ are independently a substituted or unsubstituted C1-C6 alkyl;
(c) R19 is an unsubstituted methylene:
(d) R23 and R23′ are hydrogen;
(e) R24 and R24′ are independently unsubstituted C1-C2 alkyl;
(d) R25 and R25′ are independently a triflate or halide; and
(e) the substituents, when present, are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a carbonyl, a halide, a hydroxyl, an aroxy, an alkylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof; and
wherein the cis-diol has an enantiomeric excess from about 80% to 100%, as determined by chiral HPLC.