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

doi:10.1002/anie.201508022

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

Angew Chem Int Ed Engl. 2015 Dec 14;54(51):15511-5. doi: 10.1002/anie.201508022. Epub 2015 Nov 5.

Affiliations

¹ The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan) http://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html.
² Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany).
³ Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656 (Japan).
⁴ The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan) http://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html. sasai@sanken.osaka-u.ac.jp.

PMID: 26537173
DOI: 10.1002/anie.201508022

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.

Keywords: allenes; annulations; organocatalysis; phosphines; umpolung.

Publication types

Research Support, Non-U.S. Gov't