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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Veröffentlicht in:	Organic letters 2022-10, Vol.24 (41), p.7685-7689
Hauptverfasser:	Nishimura, Kazuki, Ogura, Yoshihiro, Takeda, Kazuki, Guo, Weiwei, Ishihara, Kazuaki
Format:	Artikel
Sprache:	eng
Schlagworte:	Alanine Amides Amination Amino Acids - chemistry Catalysis Stereoisomerism
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creator	Nishimura, Kazuki Ogura, Yoshihiro Takeda, Kazuki Guo, Weiwei Ishihara, Kazuaki
description	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.
doi_str_mv	10.1021/acs.orglett.2c03249
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Lett</addtitle><date>2022-10-21</date><risdate>2022</risdate><volume>24</volume><issue>41</issue><spage>7685</spage><epage>7689</epage><pages>7685-7689</pages><issn>1523-7060</issn><eissn>1523-7052</eissn><abstract>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. 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subjects	Alanine Amides Amination Amino Acids - chemistry Catalysis Stereoisomerism
title	Chiral π–Cu(II) Catalysts for the Enantioselective α‑Amination of N‑Acyl-3,5-dimethylpyrazoles
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