SN2' alkylation of chiral allylic cyanohydrin o-phosphates with organocuprates

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Title: SN2' alkylation of chiral allylic cyanohydrin o-phosphates with organocuprates
Authors: Baeza, Alejandro | Nájera, Carmen | Sansano, Jose M.
Research Group/s: Procesos Catalíticos en Síntesis Orgánica
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica
Keywords: Cyanohydrins | Organocuprates | Copper | Allylic substitution | Asymmetric synthesis | Unsaturated nitriles | Cyanophosphates
Knowledge Area: Química Orgánica
Issue Date: 8-Jan-2007
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Citation: BAEZA CARRATALÁ, Alejandro; NÁJERA DOMINGO, Carmen; SANSANO GIL, José Miguel. "SN2' alkylation of chiral allylic cyanohydrin o-phosphates with organocuprates". European Journal of Organic Chemistry. Vol. 2007, Issue 7. ISSN 1434-193X, pp. 1101-1112
Abstract: Enantiomerically enriched cyanohydrin O-phosphates, prepared by enantioselective cyanophosphorylation of α,β-unsaturated aldehydes, react regioselectively at the γ-position with organocuprates derived from alkyl Grignard reagents and CuCN to afford chiral γ-alkyl-substituted α,β-unsaturated nitriles. The configuration of the new C–C double bond is mainly (E) when the reaction is performed at –78 °C and (Z) when it is carried out at higher temperatures (0 °C). A high level of transfer of the chirality in the new stereocentre, corresponding to a stereospecific anti attack onto the cyanophosphate, is observed. Enantiomerically enriched (E)-γ-alkylated α,β-unsaturated esters are prepared after subsequent methanolysis in a three-step sequence from the corresponding α,β-unsaturated aldehydes. In addition, the synthesis of (R)-4-methylnonan-1-ol, also known as the sex pheromone of the yellow mealworm Tenebrio molitor L, and its (S) enantiomer have been carried out in a four-step route from (E)-oct-2-enal.
Sponsor: This work has been supported by the DGES of the Spanish Ministerio de Educación y Ciencia (MEC) (CTQ2004-00808/BQU), the Generalitat Valenciana (CTIOIB/2002/320, GRUPOS03/134 and GV05/144) and the University of Alicante.
URI: http://hdl.handle.net/10045/2685
ISSN: 1434-193X
DOI: 10.1002/ejoc.200600822
Language: eng
Type: info:eu-repo/semantics/article
Peer Review: si
Publisher version: http://dx.doi.org/10.1002/ejoc.200600822
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