Catalytic Asymmetric 1,4-Addition Reactions Using α,β-Unsaturated N-Acylpyrroles as Highly Reactive Monodentate α,β-Unsaturated Ester Surrogates | doi.page

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Catalytic Asymmetric 1,4-Addition Reactions Using α,β-Unsaturated N-Acylpyrroles as Highly Reactive Monodentate α,β-Unsaturated Ester Surrogates

Journal of the American Chemical Society2004Vol. 126(24), pp. 7559–7570

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Shigeki Matsunaga, Tomofumi Kinoshita, Shigemitsu Okada, Shinji Harada, Masakatsu Shibasaki

Abstract

Synthesis and application of alpha,beta-unsaturated N-acylpyrroles as highly reactive, monodentate ester surrogates in the catalytic asymmetric epoxidation and Michael reactions are described. alpha,beta-Unsaturated N-acylpyrroles with various functional groups were synthesized by the Wittig reaction using ylide 2. A Sm(O-i-Pr)(3)/H(8)-BINOL complex was the most effective catalyst for the epoxidation to afford pyrrolyl epoxides in up to 100% yield and >99% ee. Catalyst loading was successfully reduced to as little as 0.02 mol % (substrate/catalyst = 5000). The high turnover frequency and high volumetric productivity of the present reaction are also noteworthy. In addition, a sequential Wittig olefination-catalytic asymmetric epoxidation reaction was developed, providing efficient one-pot access to optically active epoxides from various aldehydes in high yield and ee (96-->99%). In a direct catalytic asymmetric Michael reaction of hydroxyketone promoted by the Et(2)Zn/linked-BINOL complex, Michael adducts were obtained in good yield (74-97%), dr (69/31-95/5), and ee (73-95%). This represents the first direct catalytic asymmetric Michael reaction of unmodified ketone to an alpha,beta-unsaturated carboxylic acid derivative. The properties of alpha,beta-unsaturated N-acylpyrrole are also discussed. Finally, the utility of the N-acylpyrrole unit for further transformations is demonstrated.

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Abstract

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