AI Article Synopsis
- The study demonstrates a successful method for creating chiral compounds using a nickel catalyst in Grignard cross-coupling reactions involving dibenzothiophenes and dinaphthothiophene, achieving high enantioselectivity (up to 95% ee).
- The resulting compounds include 2-mercapto-1,1'-biphenyls and 2-mercapto-1,1'-binaphthyls, which were produced in high yields and have potential for further functionalization.
- Additionally, the flipping rate of dinaphthothiophene was analyzed through variable-temperature NMR, providing insights into its structural dynamics.
Article Abstract
Catalytic asymmetric Grignard cross-coupling of 1,9-disubstituted dibenzothiophenes (6a-c) and dinaphthothiophene (6d) with aryl- and alkyl-Grignard reagents (7) proceeded with high enantioselectivity (up to 95% ee) in the presence of a nickel catalyst (3-6 mol %) coordinated with 2-diphenylphosphino-1,1'-binaphthyl (H-MOP) or oxazoline-phosphine ligand (i-Pr-phox) in THF to give 2-mercapto-2'-substituted-1,1'-biphenyls (8a-c) and 2-mercapto-2'-substituted-1,1'-binaphthyls (8d) in high yields. The mercapto group in the axially chiral cross-coupling products was converted into several functional groups by way of the methylsulfinyl group. The rate of flipping in dinaphthothiophene was measured by variable-temperature (31)P NMR analysis of methylphenylphosphinyldinaphthothiophene derivative (21).
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