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Andrew D. Smith - One of the best experts on this subject based on the ideXlab platform.

  • isothiourea catalysed enantioselective pyrrolizine synthesis synthetic and computational studies
    Organic and Biomolecular Chemistry, 2016
    Co-Authors: Daniel Graham Stark, Alexandra M. Z. Slawin, James E Taylor, Patrick Williamson, Emma R Gayner, Stefania Francesca Musolino, Ryan W F Kerr, Timothy J C Oriordan, Stuart Macgregor, Andrew D. Smith
    Abstract:

    The catalytic enantioselective synthesis of a range of cis-pyrrolizine carboxylate derivatives with outstanding stereocontrol (14 examples, >95 : 5 dr, >98 : 2 er) through an isothiourea-catalyzed Intramolecular Michael Addition-lactonisation and ring-opening approach from the corresponding enone acid is reported. An optimised and straightforward three-step synthetic route to the enone acid starting materials from readily available pyrrole-2-carboxaldehydes is delineated, with benzotetramisole (5 mol%) proving the optimal catalyst for the enantioselective process. Ring-opening of the pyrrolizine dihydropyranone products with either MeOH or a range of amines leads to the desired products in excellent yield and enantioselectivity. Computation has been used to probe the factors leading to high stereocontrol, with the formation of the observed cis-steroisomer predicted to be kinetically and thermodynamically favoured.

  • enantioselective synthesis of 2 3 disubstituted trans 2 3 dihydrobenzofurans using a bronsted base thiourea bifunctional catalyst
    Organic and Biomolecular Chemistry, 2016
    Co-Authors: Diego Javier Barrios Antunez, Alexandra M. Z. Slawin, Mark D Greenhalgh, Charlene Fallan, Andrew D. Smith
    Abstract:

    The diastereo- and enantioselective synthesis of 2,3-disubstituted trans-2,3-dihydrobenzofuran derivatives (15 examples, up to 96:4 dr, 95:5 er) via Intramolecular Michael Addition has been developed using keto–enone substrates and a bifunctional tertiary amine–thiourea catalyst. This methodology was extended to include non-activated ketone pro-nucleophiles for the synthesis of 2,3-disubstituted indane and 3,4-disubstituted tetrahydrofuran derivatives.

  • stereodivergent organocatalytic Intramolecular Michael Addition lactonization for the asymmetric synthesis of substituted dihydrobenzofurans and tetrahydrofurans
    Chemistry: A European Journal, 2014
    Co-Authors: Dorine Belmessieri, Alix De La Houpliere, Ewen D D Calder, James E Taylor, Andrew D. Smith
    Abstract:

    A stereodivergent asymmetric Lewis base cata- lyzed Michael Addition/lactonization of enone acids into sub- stituted dihydrobenzofuran and tetrahydrofuran derivatives is reported. Commercially available (S)-()-tetramisole hydro- chloride gives products with high syn diastereoselectivity in excellent enantioselectivity (up to 99:1 d.r.syn/anti ,9 9 % ee syn), whereas using a cinchona alkaloid derived catalyst gives the corresponding anti-diastereoisomers as the major product (up to 10:90 d.r.syn/anti ,9 9 % ee anti).

  • organocatalytic functionalization of carboxylic acids isothiourea catalyzed asymmetric intra and intermolecular Michael Addition lactonizations
    Journal of the American Chemical Society, 2011
    Co-Authors: Dorine Belmessieri, Carmen Simal, Louis C. Morrill, Alexandra M. Z. Slawin, Andrew D. Smith
    Abstract:

    Tetramisole promotes the catalytic asymmetric Intramolecular Michael Addition−lactonization of a variety of enone acids, giving carbo- and heterocyclic products with high diastereo- and enantiocontrol (up to 99:1 dr, up to 99% ee) that are readily derivatized to afford functionalized indene and dihydrobenzofuran carboxylates. Chiral isothioureas also promote the catalytic asymmetric intermolecular Michael Addition−lactonization of arylacetic acids and α-keto-β,γ-unsaturated esters, giving anti-dihydropyranones with high diastereo- and enantiocontrol (up to 98:2 dr, up to 99% ee).

Chuchi Tang - One of the best experts on this subject based on the ideXlab platform.

Youming Wang - One of the best experts on this subject based on the ideXlab platform.

Zhenghong Zhou - One of the best experts on this subject based on the ideXlab platform.

Haibin Song - One of the best experts on this subject based on the ideXlab platform.