US 11,905,237 B2
Access to chiral bisphenol (BPOL) ligands through desymmetrizing asymmetric ortho-selective mono-halogenation
Ying-Yeung Yeung, Hong Kong (CN); Xiaodong Xiong, Nanchang (CN); Tianyu Zheng, Hong Kong (CN); Xinyan Wang, Guangdong (CN); and Ying-Lung Steve Tse, Hong Kong (CN)
Assigned to The Chinese University of Hong Kong, Hong Kong (CN)
Filed by The Chinese University of Hong Kong, Hong Kong (CN)
Filed on Mar. 25, 2021, as Appl. No. 17/212,605.
Claims priority of provisional application 63/001,929, filed on Mar. 30, 2020.
Prior Publication US 2021/0300853 A1, Sep. 30, 2021
Int. Cl. C07C 37/62 (2006.01); B01J 31/24 (2006.01); C07C 37/18 (2006.01); C07F 9/24 (2006.01); C07C 39/367 (2006.01)
CPC C07C 37/62 (2013.01) [B01J 31/2404 (2013.01); C07C 37/18 (2013.01); C07C 39/367 (2013.01); C07F 9/2404 (2013.01); C07B 2200/09 (2013.01)] 15 Claims
 
1. A method of halogenation, the method comprising contacting a reactant bisphenol with a source of a halogen in the presence of a catalyst under process conditions sufficient to prepare a halogenated bisphenol, wherein
the halogen source is bromine, N-bromosuccinimide (NBS), N-bromophthalimide (NBP), N-bromoacetamide (NBA), 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), 1,3-di bromo-5,5-diphenylhydantoin (DBDMH), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCO), chlorine, N-chlorosuccinimide (NCS), N-chlorophthalimide (NCP), 1,3-dichloro-5,5-dimethylhydantoin (DCDMH), 1,3-di chloro-5,5-diphenylhydantoin (DCDPH), 1-(4-methylbenzoyl)-3-chloro-5,5-diphenylhydantoin, iodine, or N-iodosuccinimide; and
the catalyst is N-[3,5-bis(trifluoromethyl)phenyl]-N′-[(1S,2S)-2-(dimethylamino)cyclohexyl]urea; N-[3,5-bis(trifluoromethyl)phenyl]-N′-[(1S,2S)-2-(di-n-pentylamino)cyclohexyl]urea; 3-[[3,5-bis(trifluoromethyl)phenyl]amino]-4-[[(1S,2S)-2-(dimethylamino)cyclohexyl]amino]-3-cyclobutene-1,2-dione; N-[3,5-bis(trifluoromethyl)phenyl]-N′-[(1S,2S)-2-[(11bS)-3,5-dihydro-4H-dinaphth[2,1-c:1′,2′-e]azepin-4-yl]cyclohexyl]urea; or N-[3,5-bis(trifluoromethyl)phenyl]-N′-[(1S,2S)-2-[(11bR)-3,5-dihydro-4H-dinaphth[2,1-c:1′,2′-e] azepin-4-yl]cyclohexyl]urea.