A selection of the established and recently characterized alkaloids from the exploration of plant- and some marine-associated endophytic fungi is reviewed, with reference to alkaloids of biological significance.

An overview is presented of the well-established role of alkaloids in drug discovery, the application of more sustainable chemicals, and biological approaches, and the implementation of information systems to address the current challenges faced in meeting global disease needs. The necessity for a new international paradigm for natural product discovery and development for the treatment of multidrug resistant organisms, and rare and neglected tropical diseases in the era of the Fourth Industrial Revolution and the Quintuple Helix is discussed.

The widely distributed, essential redox factor pyrroloquinoline quinone (PQQ, methoxatin) (1) was discovered in the mid-1960s. The breadth and depth of its biological effects are steadily being revealed, and understanding its biosynthesis at the genomic level is a continuing process. In this review, aspects of the chemistry, biology, biosynthesis, and commercial production of 1 at the gene level, and some applications, are presented from discovery through to mid-2021.

The profound interconnectedness of the sciences and technologies embodied in the Fourth Industrial Revolution is discussed in terms of the global role of natural products, and how that interplays with the development of sustainable and climate-conscious practices of cyberecoethnopharmacolomics within the Quintuple Helix for the promotion of a healthier planet and society.

The application of oxidative dimerization for the biomimetic synthesis of balsaminone A and ellagic acid is described. Balsaminone A is synthesized via the oxidative dimerization of 1,2,4-trimethoxynaphthalene under anhydrous conditions using CAN, PIDA in BF3 ·OEt2 or PIFA in BF3 ·OEt2 in 7–8% yields over 3 steps. Ellagic acid is synthesized from its biosynthetic precursor gallic acid, in 83% yield over 2 steps.