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. 2016 Feb 18;55(8):2929-33.
doi: 10.1002/anie.201510910. Epub 2016 Jan 25.

Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base-Free Catalytic Asymmetric C-C Bond Formation with Terminal Ynamides

Andrea M Cook  1 , Christian Wolf  2
Affiliations

Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base-Free Catalytic Asymmetric C-C Bond Formation with Terminal Ynamides

Andrea M Cook et al. Angew Chem Int Ed Engl. .

Abstract

The asymmetric addition of terminal ynamides to trifluoromethyl ketones with a readily available chiral zinc catalyst gives CF3 -substituted tertiary propargylic alcohols in up to 99 % yield and 96 % ee. The exclusion of organozinc additives and base as well as the general synthetic utility of the products are key features of this reaction. The value of the β-hydroxy-β-trifluoromethyl ynamides is exemplified by selective transformations to chiral Z- and E-enamides, an amide, and N,O-ketene acetals. The highly regioselective hydration, stereoselective reduction, and hydroacyloxylation reactions proceed with high yields and without erosion of the ee value of the parent β-hydroxy ynamides.

Keywords: enamides; homogeneous catalysis; organofluorine compounds; synthetic methods; ynamides.

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Figures

Figure 1
Figure 1
X-ray structures of (S,Z)-28 (left) and (S,E)-30 (right). Selected bond lengths for 28 [Å]: C=C: 1.325, N-C(sp2): 1.437; 30: C=C: 1.319, N-C(sp2): 1.421, O-C(sp2): 1.411.
Scheme 1
Scheme 1
Catalytic asymmetric ynamide addition to trifluoromethyl ketones provides practical access to chiral enamides, amides and N,O-ketene acetals carrying a tertiary CF3-substituted alcohol group.
Scheme 2
Scheme 2
Selective transformations of β-hydroxy ynamides.
See this image and copyright information in PMC

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