The article introduces the first copper-catalyzed highly diastereo- and enantioselective asymmetric tandem reaction for the construction of highly functionalized cyclohexane arboxylates with six stereogenic centers and ketoesters and  nitroalkenes as reactants developed by the research group headed by Prof. HUANG Hanmin of the State Key Laboratory for Oxo Synthesis and Selective Oxidation of the LICP (Angew. Chem. Int. Ed. 2012, 51, 1248 –1251). The report describes that “Cyclohexanes assemble in a domino fashion: A ketoester first forms a copper enolate intermediate, which adds one nitroalkene molecule and then another, followed by a ring-closing operation to yield a single diastereomer.” (C&EN, 2012, 90, 28)

Contiguous multiple stereocenters are a highly desirable structural motif found in natural and synthetic bioactive compounds. According to Prof. HUANG, two other groups have reported cyclohexanes with six contiguous stereocenters, but either as a by-product or in low yield and without providing the absolute structures of the compounds. A compound with eight contiguous stereocenters is also known, although two steps were needed to make it.

Just like Prof. HUANG told C&EN, their method “could be claimed to be a record for the synthesis of the most contiguous stereocenters in a molecule made in just one step.” (C&EN, 2012, 90, 28)

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Six Stereocenters Forged in One Step (Image downloaded from http://cen.acs.org/articles/90/i4/Six-Stereocenters-Forged-One-Step.html)