Insights into Stereoselectivity Switch in Michael Addition-Initiated Tandem Mannich Cyclizations and Their Extension from Enamines to Vinyl Ethers.

Both cis- and trans- tetracyclic spiroindolines are the core of many important biologically active indole alkaloids, but the divergent synthesis of these important motifs is largely hampered by the limited stereoselectivity control. A facile stereoinversion protocol is reported here in Michael addition-initiated tandem Mannich cyclizations for constructing tetracyclic spiroindolines, providing an easy access to two diastereoisomeric cores of monoterpene indole alkaloids with high selectivity. The mechanistic studies including in situ NMR experiments, control experiments, and DFT calculations reveal that the reaction undergoes a unique retro-Mannich/re-Mannich rearrangement including a C-C bond cleavage that is very rare for a saturated six-membered carbocycle. Insights into the stereoinversion process have been uncovered, and the major effects were determined to be the electronic properties of N-protecting groups of the indole with the aid of Lewis acid catalysts. By understanding these insights, the stereoselectivity switching strategy is also smoothly applied from enamine substrates to vinyl ether substrates, which are enriched greatly for the divergent synthesis and stereocontrol of monoterpene indole alkaloids. The current reaction also proves to be very practical and was successfully applied to the gram-scale total synthesis of strychnine and deethylibophyllidine in short routes.

Anionic Templates Drive Conversion between a ZnII9L6 Tricapped Trigonal Prism and ZnII6L4 Pseudo-Octahedra.

This work introduces the use of 8-aminoquinoline subcomponents to generate complex three-dimensional structures. Together with a tris(formylpyridine), 8-aminoquinoline condensed around ZnII templates to produce a tris(tridentate) ligand. This ligand is incorporated into either a tricapped trigonal prismatic ZnII9L6 structure or a pair of pseudo-octahedral ZnII6L4 diastereomers, with S4 and D2 symmetries. Introduction of a methyl group onto the aminoquinoline modulated the coordination sphere of ZnII, which favored the ZnII9L6 structure and disfavored the ZnII6L4 assembly. The tricapped trigonal prismatic ZnII9L6 architecture converted into a single ZnII6L4 cage diastereomer following the addition of a dianionic 4,4'-dinitrostilbene-2,2'-disulfonate guest. Four of these guests clustered tightly at the four windows of the ZnII6L4 cage, held in place through electrostatic interactions and hydrogen bonding, stabilize a single diastereomeric configuration with S4 symmetry.

Selectivity Switch in a Rhodium(II) Carbene Triggered Cyclopentannulation: Divergent Access to Three Polycyclic Indolines.

A selectivity switch in a RhII /carbene-triggered cyclopentannulation with catalytic InCl3 is reported for the first time, affording both diastereomers of the fused spiroindolines and an unusual bridged tetracyclic indoline in high yields with excellent selectivities. Mechanistic studies indicate an intramolecular annulation of the indole with an in situ formed aminocyclopropane. The stepwise thermal conversions from the kinetic spiroindoline to the metastable bridged indoline, and then to the thermodynamic spiroindoline, involving a ring-opening rearrangement of a cyclopentane, is crucial for selectivity control.

The contribution of socioeconomic factors to PM2.5 pollution in urban China.

PM2.5 pollution poses severe health risks to urban residents in low and middle-income countries. Existing studies have shown that the problem is affected by multiple socioeconomic factors. However, the relative contribution of these factors is not well understood, which sometimes leads to controversial controlling measures. In this study, we quantified the relative contribution of different socioeconomic factors, including the city size, industrial activities, and residents' activities, to PM2.5 pollution in urban China between 2014 and 2015 by using structural equation model (SEM). Our results showed that industrial activities contributed more to PM2.5 pollution than other factors. The city size and residents' activities also had significant impacts on PM2.5 pollution. The combined influence of all socioeconomic factors could explain between 44% and 48% of variation in PM2.5 pollution, which indicated the existence of influences from other factors such as weather conditions and outside sources of pollutants. Findings from our study can contribute to a more comprehensive understanding of the socioeconomic causes of PM2.5 pollution.

Copper-Catalyzed Enantioselective Cyclopropanation of Internal Olefins with Diazomalonates.

The first enantioselective copper catalyzed cyclopropanation of internal olefins with diazomalonates is reported. This process provides a new method for the synthesis of chiral 1,1-cyclopropane diesters. With a chiral bi-side arm bisoxazoline-copper(I) complex, the reaction performed well over a series of substrates, giving the desired products in good yields (up to 95%) and excellent enantioselectivities (90-95% ee).