期刊
ACS CATALYSIS
卷 8, 期 12, 页码 11926-11931出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b03708
关键词
bifunctional catalysis; Bronsted acid-base catalysis; alkene diamination; enantioselective; cyclic urea
资金
- National Institute of General Medical Sciences of the National Institutes of Health [GM 084333]
- Robert C. Borcer Science Undergraduate Research Fund (Xavier University)
Ureas of chiral diamines are prominent features of therapeutics, chiral auxiliaries, and intermediates in complex molecule synthesis. Although many methods for diamine synthesis are available, metal-free enantioselective alkene functionalizations to make protected 1,2- and 1,3-diamines from simple achiral starting materials are rare, and a single reagent that accesses a cross-section of each congener with high enantiomeric excess is not available. We describe a method to synthesize enantioenriched cyclic 5- and 6-membered ureas from allylic amines and an isocyanate using a C-2-symmetric bis(amidine) (BAM) catalyst that delivers N-selectivity from an ambident sulfonyl imide intermediate, overcoming electronic and steric deactivation at nitrogen. The geometry of 1,2-disubstituted alkenes is correlated to 5-exo and 6-endo cyclizations without altering alkene face selectivity, which is unexpectedly opposite that observed with O-nucleophiles. Straightforward product manipulations to diamine and imidazolidinone derivatives are underscored by the synthesis of an NK1 antagonist.
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