The direct asymmetric aldol reaction of glycinates represents an intriguing and straightforward strategy to make biologically significant chiral β‐hydroxy‐α‐amino‐acid derivatives. But it is not easy to realize the transformation due to the disruption of the reactive NH2 group of glycinates. Inspired by the enzymatic aldol reaction of glycine, we successfully developed an asymmetric aldol reaction of glycinate 5 and trifluoromethyl ketones 4 with 0.1–0.0033 mol % of chiral N‐methyl pyridoxal 7 a as the catalyst, producing chiral β‐trifluoromethyl‐β‐hydroxy‐α‐amino‐acid esters 6 in 55–82 % yields (for the syn‐diastereomers) with up to >20:1 dr and 99 % ee under very mild conditions. The reaction proceeds via a catalytic cycle similar to the enzymatic aldol reaction of glycine. Pyridoxal catalyst 7 a activates both reactants at the same time and brings them together in a specific spatial orientation, accounting for the high efficiency as well as excellent diastereo‐ and enantioselectivities.

of main observation and conclusion By using a combination of a chiral N-triflyl phosphoramide and TiCl4 as the catalyst, a new process for asymmetric intramolecular hydroalkoxylation of unactivated alkenes was developed, producing various chiral tetrahydrofuran derivatives in 51%-99% yields with 30%-71% ee's. www.cjc.wiley-vch.de

Organocatalysis In their Communication on page 20166, Guoqing Zhao, Baoguo Zhao et al. describe a highly efficient asymmetric biomimetic aldol reaction of glycinates and trifluoromethyl ketones via carbonyl catalysis.

The direct asymmetric aldol reaction of glycinates represents an intriguing and straightforward strategy to make biologically significant chiral β‐hydroxy‐α‐amino‐acid derivatives. But it is not easy to realize the transformation due to the disruption of the reactive NH2 group of glycinates. Inspired by the enzymatic aldol reaction of glycine, we successfully developed an asymmetric aldol reaction of glycinate 5 and trifluoromethyl ketones 4 with 0.1–0.0033 mol % of chiral N‐methyl pyridoxal 7 a as the catalyst, producing chiral β‐trifluoromethyl‐β‐hydroxy‐α‐amino‐acid esters 6 in 55–82 % yields (for the syn‐diastereomers) with up to >20:1 dr and 99 % ee under very mild conditions. The reaction proceeds via a catalytic cycle similar to the enzymatic aldol reaction of glycine. Pyridoxal catalyst 7 a activates both reactants at the same time and brings them together in a specific spatial orientation, accounting for the high efficiency as well as excellent diastereo‐ and enantioselectivities.

Organokatalyse In der Zuschrift auf S. 20328 beschreiben Guoqing Zhao, Baoguo Zhao et al. eine hoch effiziente asymmetrische biomimetische Aldolreaktion von Glycinaten und Trifluormethylketonen mittels Carbonyl‐Katalyse.