A concise synthesis of the Lycopodium alkaloid lycoposerramine Z is reported. Key to the strategy is a one-pot organocatalyzed Michael reaction followed by a domino Robinson annulation/intramolecular aza-Michael reaction promoted by LiOH, leading to enantiopure cis-decahydroquinolines.

The synthesis of the Lycopodium alkaloid (-)-cermizine B (1), which establishes its absolute configuration, is achieved by combining asymmetric organocatalysis and an uninterrupted eight-step reaction sequence, followed by a final reduction step. This "pot-economy" strategy provides access to the cis-phlegmarine stereoparent embedded in 1 for the first time, rapidly and on a gram-scale.

A diastereoselective synthesis of cis-5-oxodecahydroquinolines is described in which three stereocenters are generated in a one-pot reaction. The reaction involves a lithium hydroxide-promoted Robinson annulation/intramolecular aza-Michael domino process from an achiral acyclic tosylamine-tethered β-keto ester. The development and scope of this reaction was facilitated through the use of DFT-based mechanistic studies, which enabled the observed diastereodivergent course of the azacyclization to be rationalized. The varying stereochemistry and stability of the resulting decahydroquinolines was found to depend on whether a β-keto ester or ketone were embedded in the substrates undergoing aminocyclization. This synthetic approach gave access not only to both diastereomeric cis-decahydroquinolines from the same precursor, but also to the corresponding trans isomers, through an epimerization processes of the corresponding N-unsubstituted cis-5-oxodecahydroquinolines. The described methodology provides advanced building-blocks with the three relative stereochemistries required for the total synthesis of phlegmarine alkaloids.

Stimuli-responsive self-assembled monolayers (SAMs) are used to confer switchable physical, chemical, or biological properties to surfaces through the application of external stimuli. To obtain spatially and temporally tunable surfaces, we present microcontact printed SAMs of a hydroquinone molecule that are used as a dynamic interface to immobilize different functional molecules either via Diels-Alder or Michael thiol addition reactions upon the application of a low potential. In spite of the use of such reactions and the potential applicability of the resulting surfaces in different fields ranging from sensing to biomedicine through data storage or cleanup, a direct comparison of the two functionalization strategies on a surface has not yet been performed. Although the Michael thiol addition requires molecules that are commercial or easy to synthesize in comparison with the cyclopentadiene derivatives needed for the Diels-Alder reaction, the latter reaction produces more homogeneous coverages under similar experimental conditions.