(Photoredox) Organocatalysis in the Emergence of Life: Discovery, Applications, and Molecular Evolution.

ConspectusLife as we know it is built on complex and perfectly interlocking processes that have evolved over millions of years through evolutionary optimization processes. The emergence of life from nonliving matter and the evolution of such highly efficient systems therefore constitute an enormous synthetic and systems chemistry challenge. Advances in supramolecular and systems chemistry are opening new perspectives that provide insights into living and self-sustaining reaction networks as precursors for life.

The Formation of P-C Bonds Utilizing Organozinc Reagents for the Synthesis of Aryl- and Heteroaryl-Dichlorophosphines.

Aryl- and heteroaryl-dichlorophosphines are mildly and selectively made in a one-pot synthesis in moderate to good yields starting from the respective aryl bromides or five-membered heterocycles, following lithiation with BuLi, transmetalation with ZnCl, and subsequently the reaction with PCl. Selected aryl- and heteroaryl-dichlorophosphines were successfully synthesized using this reaction method and could easily be purified after isolation. The intermediate formation of the organozinc species is essential, as it prevents the formation of multiple substitution products.

Lewis Acid Directed Regioselective Metalations of Pyridazine.

Mono- or bidentate boron Lewis acids trigger a regioselective magnesiation or zincation of pyridazine in position C3 (ortho product) or C4 (meta product). The regioselectivity of the metalation was rationalized with the help of calculated pK values of both pyridazine and pyridazine/Lewis acid complexes.