Phosphine-Catalyzed β,γ-Umpolung Domino Reaction of Allenic Esters: Facile Synthesis of Tetrahydrobenzofuranones Bearing a Chiral Tetrasubstituted Stereogenic Carbon Center

Shinobu Takizawa, Kenta Kishi, Yasushi Yoshida, Steffen Mader, Fernando Arteaga Arteaga, Shoukou Lee, Manabu Hoshino, Magnus Rueping, Makoto Fujita, Hiroaki Sasai*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

94 Scopus citations

Abstract

An enantio-, diastereo-, regio-, and chemoselective phosphine-catalyzed β,γ-umpolung domino reaction of allenic esters with dienones has been developed for the first time. The designed sequence, involving oxy-Michael and Rauhut-Currier reactions, produced highly functionalized tetrahydrobenzofuranones, bearing a chiral tetrasubstituted stereogenic center, in up to 96 % ee. Domino effect: An enantio-, diastereo-, regio-, and chemoselective phosphine-catalyzed β,γ-umpolung domino reaction of allenic esters with dienones has been developed for the first time. The designed sequence involving oxy-Michael and Rauhut-Currier reactions produced highly functionalized tetrahydrobenzofuranones bearing a chiral tetrasubstituted stereogenic center in up to 96 % ee.

Original languageEnglish (US)
Pages (from-to)15511-15515
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number51
DOIs
StatePublished - Dec 14 2015

Bibliographical note

Funding Information:
This study was supported by a Grant-in-Aid for Scientific Research on Innovative Areas-Advanced Molecular Transformations by Organocatalysis-from The Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, the CREST project of the Japan Science and Technology Corporation (JST), and JST Advance Catalytic Transformation Program for Carbon Utilization (ACT-C). We thank the Deutsche Forschungsgemeinschaft (scholarship for S.M., International Research Training Group "Selectivity in Chemo- and Biocatalysis", SeleCa, Germany) and the JSPS Japanese-German Graduate Externship. We acknowledge the technical staff of the Comprehensive Analysis Center of ISIR, Osaka University (Japan).

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

  • allenes
  • annulations
  • organocatalysis
  • phosphines
  • umpolung

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

Fingerprint

Dive into the research topics of 'Phosphine-Catalyzed β,γ-Umpolung Domino Reaction of Allenic Esters: Facile Synthesis of Tetrahydrobenzofuranones Bearing a Chiral Tetrasubstituted Stereogenic Carbon Center'. Together they form a unique fingerprint.

Cite this