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Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-alkenylation of beta-ketoesters.
J Am Chem Soc. 2008 Apr 02; 130(13):4492-6.JA

Abstract

Construction of a nonracemic all-carbon quaternary stereocenter at the alpha-position of beta-ketoesters was achieved by way of an indium(III)-catalyzed diastereoselective alpha-alkenylation reaction of chiral enamines with 1-alkynes. The enamine bearing a chiral auxiliary derived from l-isoleucine was added to the alkyne to give an alpha-alkenylated product in excellent yield and with a stereoselectivity better than 90% ee. One can ascribe the high selectivity to a chelate intermediate involving the auxiliary and the metal atom and the high yield to efficient interactions between the indium(III) atom and the alkyne. The selectivity increased as the reaction temperature was raised to 120 degrees C and decreased at higher temperatures.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Fujimoto T
Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Endo K
No affiliation info available
Tsuji H
No affiliation info available
Nakamura M
No affiliation info available
Nakamura E
No affiliation info available

MeSH

AlkylationAlkynesAminesCarbonCatalysisEstersIndiumKetonesMolecular StructureOrganometallic CompoundsStereoisomerismZinc

Pub Type(s)

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

Language

eng

PubMed ID

18331035

Citation

Fujimoto, Taisuke, et al. "Construction of a Chiral Quaternary Carbon Center By Indium-catalyzed Asymmetric Alpha-alkenylation of Beta-ketoesters." Journal of the American Chemical Society, vol. 130, no. 13, 2008, pp. 4492-6.
Fujimoto T, Endo K, Tsuji H, et al. Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-alkenylation of beta-ketoesters. J Am Chem Soc. 2008;130(13):4492-6.
Fujimoto, T., Endo, K., Tsuji, H., Nakamura, M., & Nakamura, E. (2008). Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-alkenylation of beta-ketoesters. Journal of the American Chemical Society, 130(13), 4492-6. https://doi.org/10.1021/ja710408f
Fujimoto T, et al. Construction of a Chiral Quaternary Carbon Center By Indium-catalyzed Asymmetric Alpha-alkenylation of Beta-ketoesters. J Am Chem Soc. 2008 Apr 2;130(13):4492-6. PubMed PMID: 18331035.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-alkenylation of beta-ketoesters. AU - Fujimoto,Taisuke, AU - Endo,Kohei, AU - Tsuji,Hayato, AU - Nakamura,Masaharu, AU - Nakamura,Eiichi, Y1 - 2008/03/11/ PY - 2008/3/12/pubmed PY - 2008/4/26/medline PY - 2008/3/12/entrez SP - 4492 EP - 6 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 130 IS - 13 N2 - Construction of a nonracemic all-carbon quaternary stereocenter at the alpha-position of beta-ketoesters was achieved by way of an indium(III)-catalyzed diastereoselective alpha-alkenylation reaction of chiral enamines with 1-alkynes. The enamine bearing a chiral auxiliary derived from l-isoleucine was added to the alkyne to give an alpha-alkenylated product in excellent yield and with a stereoselectivity better than 90% ee. One can ascribe the high selectivity to a chelate intermediate involving the auxiliary and the metal atom and the high yield to efficient interactions between the indium(III) atom and the alkyne. The selectivity increased as the reaction temperature was raised to 120 degrees C and decreased at higher temperatures. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/18331035/Construction_of_a_chiral_quaternary_carbon_center_by_indium_catalyzed_asymmetric_alpha_alkenylation_of_beta_ketoesters_ DB - PRIME DP - Unbound Medicine ER -