Asymmetric Total Synthesis of the 1- e pi -Aglycon of the Cripowellins A and B
| Autor: | Gerhard Raabe, Carsten F. Janeck, Achim Lenzen, Kelly Catlin, Jan Runsink, Michael Backes, Marie-Isabelle Lannou, Dieter Enders |
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| Přispěvatelé: | Information Security and Cryptography Group. (IS&C), Saarland University [Saarbrücken], Synthèse et électrosynthèse organiques (SESO), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Rheinisch-Westfälische Technische Hochschule Aachen (RWTH), Cibles Thérapeutiques et conception de médicaments (CiTCoM - UMR 8038), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP) |
| Jazyk: | angličtina |
| Rok vydání: | 2005 |
| Předmět: |
Alkylation
010405 organic chemistry Chemistry Stereochemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry Organic Chemistry Enantioselective synthesis Total synthesis Stereoisomerism 010402 general chemistry Metathesis 01 natural sciences Radical cyclization 0104 chemical sciences 3. Good health Alkaloids Cyclization Dihydroxylation Intramolecular force Heck reaction Electrophile Amaryllidaceae Alkaloids [CHIM]Chemical Sciences ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Organic Chemistry Journal of Organic Chemistry, American Chemical Society, 2005, 70 (25), pp.10538-10551. ⟨10.1021/jo0518093⟩ |
| ISSN: | 0022-3263 1520-6904 |
| DOI: | 10.1021/jo0518093⟩ |
| Popis: | [structure: see text] The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epi-aglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee > or = 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47. |
| Databáze: | OpenAIRE |
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