Enantiospecific Synthesis of a Protected Equivalent of APTO, the β-Amino Acid Fragment of Microsclerodermins C and D, by Aziridino-γ-lactone Methodology
Enantiospecific Synthesis of a Protected Equivalent of APTO, the β-Amino Acid Fragment of Microsclerodermins C and D, by Aziridino-γ-lactone Methodology
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DOI：
10.1002/ejoc.200801000
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发表时间：
2009-02-01
影响因子：
2.8
通讯作者：
Dodd, Robert H.
中科院分区：
文献类型：
--
作者：
Tarrade-Matha, Aurelie;Valle, Marcelo Siqueira;Dodd, Robert H.
The efficient synthesis of a protected form of (2S,3R,4S,5S,7E)-3-amino-8-phenyl-2,4,5-trihydroxyoct-7-enoic acid (APTO), the alpha-hydroxy beta-amino acid component of microsclerodermins C and D, 23-membered cyclic peptides isolated from lithistid sponges, is described. The strategy is based on the preparation of the aziridino-gamma-lactone 46 from L-gulose by a procedure previously developed in our laboratory for simpler substrates. Regioselective opening of the aziridine at C-2 by acetate anion, an intrinsic reactivity pattern of aziridino-gamma-lactones, followed by a Heck reaction to install the terminal phenyl group, provides lactone 48. This, a lactonized form of APTO, can be considered an activated building block for the synthesis of microsclerodermins C and D or their analogues, as demonstrated by its subsequent reaction with a benzylamine to give the carboxamide 51. This represents the first example of the use of an aziridino-gamma-lactone for the stereoselective synthesis of an a alpha-substituted beta-amino acid derivative. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
