Desymmetrization and Parallel Kinetic Resolution of 1-Ethynylcyclobutanols via Asymmetric Cooperative Gold Catalysis.

Enantioselective gold catalysis remains a challenging area of research. By harnessing gold-ligand cooperation in the presence of a chiral bifunctional phosphine ligand featuring a novel 3'-phosphine oxide moiety, highly enantioselective desymmetrization of 1-ethynylcyclobutanols is achieved, permitting access to chiral α-methylenecyclopentanones featuring a diverse array of chiral quaternary and tertiary centers. This cooperative gold catalysis also enables parallel kinetic resolution in gold catalysis, delivering cyclopentanone regioisomers with excellent enantiomeric excesses. DFT calculations of the transition states support the distinct mechanism of asymmetric induction via controlling the conformation of the bound substrate and hence dictating the ring bond undergoing migration.

Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis.

A gold(I)-catalyzed enantioselective dearomatization is achieved via metal-chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl-2-ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1-naphthols, 2-naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.

Wheat genotypes with higher yield sensitivity to drought overproduced proline and lost minor biomass under severer water stress.

To clarify the differences in growth and yield responses to drought stress among genotypes contrasting in environmental background, dryland and irrigated genotypes, as well as the underlying biochemical mechanism would provide valuable information for developing superior dryland cultivars. Pot experiments for the whole life cycle in fifteen genotypes and comparative metabolomics analysis for seedlings between two drought tolerant (DT) dryland genotypes and two drought sensitive (DS) irrigated ones were carried out. The DT dryland genotypes suffered heavy biomass loss during severer drought but showed minor yield loss ultimately, while the DS irrigated ones showed minor biomass loss but greater yield loss. Additionally, the superior DT dryland genotypes showed better yield performance under both drought stress and well-watered conditions, indicating their possessing both drought tolerance and high yield potential traits. Suffering severer drought stress, seedling leaves of the DS irrigated genotypes increased some amino acids and organic acids to maintain cell metabolism and accumulate more biomass. Proline in particular was overproduced, which might cause toxicity to cell systems and lead to enormous yield loss ultimately. In contrast, DT dryland genotypes increased the beneficial amino acid and phenolic acids to enhance cell self-protection for alleviating drought damage and efficiently minimized yield loss ultimately.

Gold-Catalyzed Synthesis of Chiral Cyclopentadienyl Esters via Chirality Transfer.

Efficient access to chiral cyclopentadienyl esters from readily accessible chiral enynyl ester substrates is developed. Typically high levels of chirality transfer realized in this homogeneous gold catalysis are attributed to the intermediacy of a chiral bent allene gold complex. Cyclopentadienyl esters can be prepared in good yields and with excellent enantiomeric excesses. The synthetic utilities of the chiral cyclopentadienyl esters are demonstrated by the Diels-Alder reactions, fluorination, alkylation, and epoxidation without any notable erosion of enantiopurity.

Stomatal conductance bears no correlation with transpiration rate in wheat during their diurnal variation under high air humidity.

A good understanding of the response of photosynthesis rate (P N) and transpiration rate (Tr) to stomatal alteration during the diurnal variations is important to cumulative photosynthetic production and water loss of crops. Six wheat genotypes were studied for 2 years with pot cultivation in rain-shelter. Among different genotypes, stomatal conductance (g s) was significantly correlated with both P N and Tr. But for each genotype, though g s was significantly correlated with P N regardless of relative air humidity (RH) status and it was also significantly correlated with Tr under lower RH (LRH, 15.4%) and moderate RH (MRH, 28.3%), it was not correlated with Tr under higher RH (HRH, 36.7%) during the diurnal changes. The conditional correlation between g s and Tr of wheat evoked new thinking on the relationships among g s, P N and Tr. Path analysis was further carried out to clarify the correlations of g s with the four atmospheric factors, that of Tr with g s and the four factors and the direct and indirect effects of the factors, during their diurnal dynamic variation. The effects of these factors on g s or Tr were related to RH. All the four factors had a much higher correlation with g s under HRH than that under LRH and MRH. Air temperature (T) had a rather higher direct effect than RH and photosynthetically active radiation (PAR). Also, the other factors had a much higher indirect effect on g s through vapor pressure deficit (VPD) and T. Transpiration rate was highly correlated with g s under LRH and MRH, with g s having a higher direct effect on it. In comparison, Tr was not correlated with g s under HRH but highly correlated with the atmospheric factors, with T, RH, and PAR having a higher indirect effect through VPD.