Chiral π–Cu(II) Catalysts for the Enantioselective α‑Amination of N‑Acyl-3,5-dimethylpyrazoles

We report the highly enantioselective α-amination of N-acyl-3,5-dimethylpyrazoles with dialkyl azodicarboxylates, catalyzed by in situ generated π–Cu­(II) complexes that consist of Cu­(OTf)2 and N-(5H-dibenzo­[a,d]­[7]­annulen-5-yl)-l-alanine-derived amides, to give the corresponding products as d-α...

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Bibliographic Details
Published inOrganic letters Vol. 24; no. 41; pp. 7685 - 7689
Main Authors Nishimura, Kazuki, Ogura, Yoshihiro, Takeda, Kazuki, Guo, Weiwei, Ishihara, Kazuaki
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 21.10.2022
Amer Chemical Soc
Subjects
Alanine
Amides
Amination
Amino Acids - chemistry
Catalysis
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
Stereoisomerism
KETONES
CYCLOADDITION
DESIGN
1,3-DICARBONYL COMPOUNDS
CYANOACETATES
COMPLEXES
ELECTROPHILIC AMINATION
PROPIOLOYLPYRAZOLES
CATION
DERIVATIVES
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Summary:We report the highly enantioselective α-amination of N-acyl-3,5-dimethylpyrazoles with dialkyl azodicarboxylates, catalyzed by in situ generated π–Cu­(II) complexes that consist of Cu­(OTf)2 and N-(5H-dibenzo­[a,d]­[7]­annulen-5-yl)-l-alanine-derived amides, to give the corresponding products as d-α-amino acid derivatives (up to >99% yield and 99% ee). The site-selectivity and enantioselectivity can be satisfactorily explained by the coordination of dialkyl azodicarboxylate with π–Cu­(II) complex. The synthetic potential of this one-pot transformation to the α-amino ester is also described.
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ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.2c03249