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Catalytic asymmetric 1,4-addition reactions using alpha,beta-unsaturated N-acylpyrroles as highly reactive monodentate alpha,beta-unsaturated ester surrogates.
J Am Chem Soc. 2004 Jun 23; 126(24):7559-70.JA

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.

Authors+Show Affiliations

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

15198603

Citation

Matsunaga, Shigeki, et al. "Catalytic Asymmetric 1,4-addition Reactions Using Alpha,beta-unsaturated N-acylpyrroles as Highly Reactive Monodentate Alpha,beta-unsaturated Ester Surrogates." Journal of the American Chemical Society, vol. 126, no. 24, 2004, pp. 7559-70.
Matsunaga S, Kinoshita T, Okada S, et al. Catalytic asymmetric 1,4-addition reactions using alpha,beta-unsaturated N-acylpyrroles as highly reactive monodentate alpha,beta-unsaturated ester surrogates. J Am Chem Soc. 2004;126(24):7559-70.
Matsunaga, S., Kinoshita, T., Okada, S., Harada, S., & Shibasaki, M. (2004). Catalytic asymmetric 1,4-addition reactions using alpha,beta-unsaturated N-acylpyrroles as highly reactive monodentate alpha,beta-unsaturated ester surrogates. Journal of the American Chemical Society, 126(24), 7559-70.
Matsunaga S, et al. Catalytic Asymmetric 1,4-addition Reactions Using Alpha,beta-unsaturated N-acylpyrroles as Highly Reactive Monodentate Alpha,beta-unsaturated Ester Surrogates. J Am Chem Soc. 2004 Jun 23;126(24):7559-70. PubMed PMID: 15198603.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalytic asymmetric 1,4-addition reactions using alpha,beta-unsaturated N-acylpyrroles as highly reactive monodentate alpha,beta-unsaturated ester surrogates. AU - Matsunaga,Shigeki, AU - Kinoshita,Tomofumi, AU - Okada,Shigemitsu, AU - Harada,Shinji, AU - Shibasaki,Masakatsu, PY - 2004/6/17/pubmed PY - 2004/10/13/medline PY - 2004/6/17/entrez SP - 7559 EP - 70 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 24 N2 - 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. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15198603/Catalytic_asymmetric_14_addition_reactions_using_alphabeta_unsaturated_N_acylpyrroles_as_highly_reactive_monodentate_alphabeta_unsaturated_ester_surrogates_ L2 - https://doi.org/10.1021/ja0485917 DB - PRIME DP - Unbound Medicine ER -