Chiral aldehyde catalysis is a burgeoning strategy for the catalytic asymmetric α-functionalization of aminomethyl compounds. However, the reaction types are limited and to date include no examples of stereodivergent catalysis. In this work, we disclose two chiral aldehyde-catalysed diastereodivergent reactions: a 1,6-conjugate addition of amino acids topara-quinone methides and a bio-inspired Mannich reaction of pyridinylmethanamines and imines. Both thesyn- andanti-products of these two reactions can be obtained in moderate to high yields, diastereo- and enantioselectivities. Four potential reaction models produced by DFT calculations are proposed to explain the observed stereoselective control. Our work shows that chiral aldehyde catalysis based on a reversible imine formation principle is applicable for the α-functionalization of both amino acids and aryl methylamines, and holds potential to promote a range of asymmetric transformations diastereoselectively.

Sustainability is becoming increasingly important in the world we live in, because of the rapid global population growth and climate change (drought, extreme temperature fluctuations). People in developing countries need more sustainable protein sources instead of the traditional, less sustainable meat, fish, egg, and dairy products. Alternative sources (plant-based, such as grains (wheat, rice sorghum), seeds (chia, hemp), nuts (almond, walnut), pulses (beans, lentil, pea, lupins), and leaves (duckweed), as well as mycoproteins, microalgae, and insects) can compensate for the increased demand for animal protein. In this context, our attention has been specifically focused on duckweed—which is the third most important aquatic plant after the microalgae Chlorella and Spirulina—to explore its potential for use in a variety of areas, particularly in the food industry. Duckweed has special properties: It is one of the fastest-growing plants in the world (in freshwater), multiplying its mass in two days, so it can cover a water surface quickly even in filtered sunlight (doubling its biomass in 96 hours). During this time, it converts a lot of carbon dioxide into oxygen. It is sustainable, environmentally friendly (without any pesticides), and fast growing; can be grown in indoor vertical farms and aquaculture, so it does not require land; is easy to harvest; and has a good specific protein yield. Duckweed belongs to the family Araceae, subfamily Lemnoideae, and has five genera (Lemna, Spirodela, Wolffia, Wolffiella, Landolita) containing a total of approximately 36–38 recognised species. Duckweed is gaining attention in nutrition and food sciences due to its potential as a sustainable source of protein, vitamins, minerals, and other bioactive compounds. However, there are several gaps in research specifically focused on nutrition and the bioaccessibility of its components. While some studies have analysed the variability in the nutritional composition of different duckweed species, there is a need for comprehensive research on the variability in nutrient contents across species, growth conditions, harvesting times, and geographic locations. There has been limited research on the digestibility, bioaccessibility (the proportion of nutrients that are released from the food matrix during digestion), and bioavailability (the proportion that is absorbed and utilised by the body) of nutrients in duckweed. Furthermore, more studies are needed to understand how food processing (milling, fermentation, cooking, etc.), preparation methods, and digestive physiology affect the nutritional value and bioavailability of the essential bioactive components in duckweed and in food matrices supplemented with duckweed. This could help to optimise the use of duckweed in human diets (e.g., hamburgers or pastas supplemented with duckweed) or animal feed. More research is needed on how to effectively incorporate duckweed into diverse cuisines and dietary patterns. Studies focusing on recipe development, consumer acceptance, palatability, and odour are critical. Addressing these gaps could provide valuable insights into the nutritional potential of duckweed and support its promotion as a sustainable food source, thereby contributing to food security and improved nutrition. In summary, this article covers the general knowledge of duckweed, its important nutritional values, factors that may affect their biological value, and risk factors for the human diet, while looking for technological solutions (covering traditional and novel technologies) that can be used to increase the release of the useful, health-promoting components of duckweed and, thus, their bioavailability. This article, identifying gaps in recent research, could serve as a helpful basis for related research in the future. Duckweed species with good properties could be selected by these research studies and then included in the human diet after they have been tested for food safety.

Potassium tert-butoxide-promoted aerobic oxidation of N-alkyl iminium salts is reported. The reaction is atom-economical and environmentally friendly. Iminium salts derived from isoquinoline, quinoline, phenanthridine, phenanthroline, and phthalazine were successfully transformed into their corresponding unsaturated lactams with up to 95% yield under mild conditions in the absence of photocatalysts and metallic or organic catalysts. Owing to the general substrate scope, low cost, feasibility of scale up, wide availability of reagents, and green reaction conditions, this method shows great potential for preparing isoquinolones and related compounds. The method was applied for atom- and step-economical total synthesis of natural products such as norketoyobyrine.

The combined catalytic systems derived from organocatalysts and transition metals exhibit powerful activation and stereoselective-control abilities in asymmetric catalysis. This work describes a highly efficient chiral aldehyde-nickel dual catalytic system and its application for the direct asymmetric α−propargylation reaction of amino acid esters with propargylic alcohol derivatives. Various structural diversity α,α−disubstituted non-proteinogenic α−amino acid esters are produced in good-to-excellent yields and enantioselectivities. Furthermore, a stereodivergent synthesis of natural product NP25302 is achieved, and a reasonable reaction mechanism is proposed to illustrate the observed stereoselectivity based on the results of control experiments, nonlinear effect investigation, and HRMS detection.

Catalytic asymmetric Tsuji–Trost benzylation is a promising strategy for the preparation of chiral benzylic compounds. However, only a few such transformations with both good yields and enantioselectivities have been achieved since this reaction was first reported in 1992, and its use in current organic synthesis is restricted. In this work, we use N-unprotected amino acid esters as nucleophiles in reactions with benzyl alcohol derivatives. A ternary catalyst comprising a chiral aldehyde, a palladium species, and a Lewis acid is used to promote the reaction. Both mono- and polycyclic benzyl alcohols are excellent benzylation reagents. Various unnatural optically active α-benzyl amino acids are produced in good-to-excellent yields and with good-to-excellent enantioselectivities. This catalytic asymmetric method is used for the formal synthesis of two somatostatin mimetics and the proposed structure of natural product hypoestestatin 1. A mechanism that plausibly explains the stereoselective control is proposed.