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AldehydesQ 0320 DOI: 10.1002/chin.201106078

Catalytic Asymmetric Claisen Rearrangement of Unactivated Allyl Vinyl Ethers. — The presence of the free hydroxy-group in the chiral catalyst is crucial. C6 Aryl substrates lead to the mostly inseparable mixtures of the anti-rearrangement [3,3]-rear-rangement products with high enantioselectivity and the products of the [1,3]sigma-tropic shifts (III). The method is not applicable to the C6-alkyl substrates [cf. (IV)] as only [1,3]-rearrangement product (V) is obtained. Diastereoselective outcome of the reaction also strongly depends on the substrate olefin geometry [cf. (VI), (VIII)]. — (GEHERTY, M. E.; DURA, R. D.; NELSON*, S. G.; J. Am. Chem. Soc. 132 (2010) 34, 11875-11877, http://dx.doi.org/10.1021/ja1039314 ; Dep. Chem., Univ. Pittsburgh, Pittsburgh, PA 15260, USA; Eng.) — Y. Steudel

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ChemInform 2011, 42, issue 06 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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ChemInform 2011, 42, issue 06 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim