Catalytic asymmetric phase-transfer reactions using tartrate-derived asymmetric two-center organocatalysts

Takashi Ohshima, Tomoyuki Shibuguchi, Yuhei Fukuta, Masakatsu Shibasaki

Research output: Contribution to journalArticle

109 Citations (Scopus)

Abstract

A new highly versatile asymmetric two-center catalyst, tartrate-derived diammonium salt (TaDiAS), was designed and a catalyst library containing more than 70 new two-center catalysts was constructed. A variety of (S,S)- and (R,R)-TaDiAS were easily synthesized from diethyl L- and D-tartrate, respectively, using common and inexpensive reagents under operationally simple reaction conditions. TaDiAS was used in phase-transfer alkylations and Michael additions to afford various optically active α-amino acid equivalents in up to 93% yield. Moreover, dramatic counter anion effects were observed in phase-transfer catalysis (PTC) for the first time, making it possible to further improve reactivity and selectivity. These findings validate the usefulness of three-dimensional fine-tuning of the catalyst (acetal, Ar, and counter anion) for optimization. Recovery and reuse of the catalyst was also possible using simple procedures. The present asymmetric PTC was successfully applied to enantioselective syntheses of serine protease inhibitor aeruginosin 298-A and its analogues.

Original languageEnglish
Pages (from-to)7743-7754
Number of pages12
JournalTetrahedron
Volume60
Issue number35
DOIs
Publication statusPublished - Aug 23 2004
Externally publishedYes

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Catalysts
Salts
Catalysis
Anions
Acetals
Serine Proteinase Inhibitors
Alkylation
Libraries
Amino Acids
Tuning
tartaric acid
Recovery
aeruginosin 298-A

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Catalytic asymmetric phase-transfer reactions using tartrate-derived asymmetric two-center organocatalysts. / Ohshima, Takashi; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Shibasaki, Masakatsu.

In: Tetrahedron, Vol. 60, No. 35, 23.08.2004, p. 7743-7754.

Research output: Contribution to journalArticle

Ohshima, Takashi ; Shibuguchi, Tomoyuki ; Fukuta, Yuhei ; Shibasaki, Masakatsu. / Catalytic asymmetric phase-transfer reactions using tartrate-derived asymmetric two-center organocatalysts. In: Tetrahedron. 2004 ; Vol. 60, No. 35. pp. 7743-7754.
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