Nature knows best: An amazing reaction cascade is uncovered by design and discovery

The Daphniphyllum alkaloids are a group of highly complex polycyclic alkaloids. Examination of the structures if several members of this family of natural products led to a hypothesis about their mode of biosynthesis (depicted in Scheme SI). Based on this hypothetical biosynthetic pathway, a laboratory synthesis was designed that incorporated as a key transformation the novel one-pot transformation of dialdehyde 24 to pentacyclic unsaturated amine 25. This process turned out to be an exceptionally efficient way to construct the pentacyclic nucleus of the Daphniphyllum alkaloids. However, a purely fortuitous discovery, resulting from accidental use of methylamine rather than ammonia, led to a great improvement in the synthesis and suggests an even more attractive possible biosynthesis.

The best thermoelectric.

What electronic structure provides the largest figure of merit for thermoelectric materials? To answer that question, we write the electrical conductivity, thermopower, and thermal conductivity as integrals of a single function, the transport distribution. Then we derive the mathematical function for the transport distribution, which gives the largest figure of merit. A delta-shaped transport distribution is found to maximize the thermoelectric properties. This result indicates that a narrow distribution of the energy of the electrons participating in the transport process is needed for maximum thermoelectric efficiency. Some possible realizations of this idea are discussed.