Asymmetric Synthesis of β‐Substituted α‐Methylenebutyro‐ lactones via TRIP‐Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)‐(−)‐Hydroxymatairesinol. Issue 13 (29th August 2013)

• Record Type: Journal Article
• Authors: Fuchs, Michael; Schober, Markus; Orthaber, Andreas; Faber, Kurt
• Is Part Of: Advanced synthesis & catalysis. Volume 355:Issue 13(2013)
• Page Start: 2499
• Page End: 2505
• Publication Date: 2013-08-29
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201300392
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)‐allylbutyrolactone species catalyzed by a chiral BINOL‐type phosphoric acid gave β‐substituted α‐methylenebutyrolactones in 68 to &gt;99% <italic>ee</italic> and 52–91% isolated yield. DFT studies on the intermediate Zn²⁺‐complex – crucial for chiral induction – suggest a six‐membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product (<italic>S</italic>)‐(−)‐hydroxymatairesinol.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg3h7zqtfw" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>