Open AccessEnantioselective Iridium-Catalyzed Allylation of Nitroalkanes: Entry to β-Stereogenic α-Quaternary Primary Amines
Author(s) -
WooOk Jung,
Binh Khanh,
Brian J. Spinello,
Zachary J. Dubey,
Seung Wook Kim,
Craig E. Stivala,
Jason R. Zbieg,
Peng Liu,
Michael J. Krische
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c05212
Subject(s) - chemistry , stereocenter , enantioselective synthesis , allylic rearrangement , iridium , nucleophile , medicinal chemistry , steric effects , catalysis , stereochemistry , organic chemistry
The first systematic study of simple nitronate nucleophiles in iridium-catalyzed allylic alkylation is described. Using a tol-BINAP-modified π-allyliridium C , O -benzoate catalyst, α,α-disubstituted nitronates substitute racemic branched alkyl-substituted allylic acetates, thus providing entry to β-stereogenic α-quaternary primary amines. DFT calculations reveal early transition states that render the reaction less sensitive to steric effects and distinct trans-effects of diastereomeric chiral-at-iridium π-allyl complexes that facilitate formation of congested tertiary-quaternary C-C bonds.