Functionalized BINOL Derivatives as Ligands for Enantioselectively Catalyzed Aldol Additions: Highly Enantioselective Synthesis of Chiral β-Hydroxy Thioesters

Reinhold Zimmer; Luise Schefzig; Anke Peritz; Vjekoslav Dekaris; Hans-Ulrich Reissig

doi:10.1055/s-2004-822364

PAPER

Functionalized BINOL Derivatives as Ligands for Enantioselectively Catalyzed Aldol Additions: Highly Enantioselective Synthesis of Chiral β-Hydroxy Thioesters

Reinhold Zimmer*^a, Luise Schefzig^a, Anke Peritz^b, Vjekoslav Dekaris^a, Hans-Ulrich Reissig^a
^a Institut für Chemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany
Fax: +49(30)83855367; e-Mail: rzimmer@chemie.fu-berlin.de;
^b Institut für Organische Chemie, Technische Universität Dresden, 01062 Dresden, Germany

Abstract

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Abstract

A series of 3,3′-disubstituted and 6,6′-disubstituted BINOL derivatives was synthesized and examined in typical titanium(IV) promoted aldol reactions. The model reaction of S-ketene silyl acetal 13 and aldehydes 12a and 12b revealed that 6,6′-dibromo-BINOL derivative (R)-6 is the ligand of choice for these transformations. Up to 97% yield with excellent enantioselectivity (ee > 97%) could be achieved. Scope and limitations were demonstrated using a series of aldehydes as substrates, which were generally transformed into their aldol adducts by the (R)-6/Ti(Oi-Pr)₄ catalyst with good efficacy and high enantioselectivity.

Keywords

binaphthalene - Aldol reaction - titanium - Sonogashira reaction - thioesters - bissteroidal ligand

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