The one-pot, organocatalytic Hayashi sequential reaction (HSR) of β-nitroacrylate, aldehyde, toluenethiol, and ethyl 2-(diethoxyphosphoryl)acrylate allowed the synthesis of almost stereoisomerically pure, highly functionalized polysubstituted cyclohexanes with very high diastereo-and enantioselectivity (up to Ͼ 99 % ee). The one-pot synthesis consists of the tertiary amine modified diarylprolinol silyl ether-mediated asymmetric Michael reaction, a domino Michael reaction/Horner-Wadsworth-Emmons reaction, and a sulfaMichael reaction. In addition, we have also demonstrated an improved protocol for the domino oxa-Michael/aldol reaction
A highly enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated aldehydes with excellent enantioselectivities (up to Ͼ99 % ee) has been developed, and this improved method offers substantial advantages over traditional approaches, not only by avoiding the use of acids or bases, but also in terms of the higher level of stereoselectivity. In addition, we have demonstrated through a plausible
This improved method offers substantial advantages over traditional approaches such as avoiding the use of acids or bases and the high level of stereoselectivity.
Recyclable Tertiary Amine Modified Diarylprolinol Ether as Aminocatalyst for the Sequential Asymmetric Synthesis of Functionalized Cyclohexanes and Chromenes. -A combined prolinol silyl ether-o-nitrobenzoic acid organocatalyst is successfully applied in the one-pot reaction of aldehydes (I) with β-nitroacrylate (II), phosphoryl acrylate (III) and toluenethiol (IV) to give highly functionalized cyclohexane derivatives (V) in high to excellent stereoselectivities (up to > 98% d.e. and > 99% e.e.). Additionally, the novel catalyst system can be used to improve domino oxa-Michael-aldol reaction of salicylic aldehydes (VI) with α,β-unsaturated aldehydes (VII). -(SHEN, H.; YANG*, K.-F.; SHI, Z.-H.; JIANG, J.-X.; LAI, G.-Q.; XU, L.-W.; Eur. J. Org. Chem. 2011, 26, 5031-5038, http://dx.
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