Women in Natural Sciences (WiNS) at ETH Zurich Celebrates its 10th Anniversary - A Retrospective and Outlook.

For this CHIMIA special issue on the United Nations Sustainable Development Goals (SDGs) and the coincidental 10th anniversary of the association of Women in Natural Sciences (WiNS) at ETH Zurich, there is no better opportunity to share what we have achieved in the last decade. WiNS was originally founded by female PhD students and PostDocs at the Department of Chemistry and Applied Biosciences (D-CHAB) and has expanded to include three additional departments at ETH Zurich. Join us in celebrating our anniversary, reflecting on what we and other associations with the same mission have done to promote gender equality and reduced inequalities for all. We invite you to reflect on what yet has to be done to enact a systemic change towards achieving equal opportunities for all, rather than simply accommodating the female perspective to Switzerland's predominantly masculine working culture.

Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic.

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new implications in retrosynthetic analysis. However, such a transformation requires the selective cleavage of highly inert chemical bonds and formation of stable intermediates amenable to further synthetic elaborations, hence its development has remained considerably challenging. Here we introduce a skeletal metalation strategy that allows lactams, a prevalent motif in bioactive molecules, to be readily converted into well-defined, synthetically useful organonickel reagents. The reaction features a selective activation of unstrained amide C-N bonds mediated by an easily prepared Ni(0) reagent, followed by CO deinsertion and dissociation under mild room temperature conditions in a formal carbonyl-to-nickel-exchange process. The underlying principles of this unique reactivity are rationalized by organometallic and computational studies. The skeletal metalation is further applied to a direct CO excision reaction and a carbon isotope exchange reaction of lactams, underscoring the broad potential of metal-carbon exchange logic in organic synthesis.

The advent of electrophilic hydroxylamine-derived reagents for the direct preparation of unprotected amines.

Electrophilic aminating reagents have seen a renaissance in recent years as effective nitrogen sources for the synthesis of unprotected amino functionalities. Based on their reactivity, several noble and non-noble transition metal catalysed amination reactions have been developed. These include the aziridination and difunctionalisation of alkenes, the amination of arenes as well as the synthesis of aminated sulfur compounds. In particular, the use of hydroxylamine-derived (N-O) reagents, such as PONT (PivONH3OTf), has enabled the introduction of unprotected amino groups on various different feedstock compounds, such as alkenes, arenes and thiols. This strategy obviates undesired protecting-group manipulations and thus improves step efficiency and atom economy. Overall, this feature article gives a recent update on several reactions that have been unlocked by employing versatile hydroxylamine-derived aminating reagents, which facilitate the generation of unprotected primary, secondary and tertiary amino groups.

Synthesis of N-Alkyl Anilines from Arenes via Iron-Promoted Aromatic C-H Amination.

We report both an intermolecular C-H amination of arenes to access N-methylanilines and an intramolecular variant for the synthesis of tetrahydroquinolines. A newly developed, highly electrophilic aminating reagent was key for the direct synthesis of unprotected N-methylanilines from simple arenes. The reactions display a broad functional group tolerance and employ catalytic amounts of a benign iron salt under mild reaction conditions.

A Late-Stage Functionalization Approach to Derivatives of the Pyrano[3,2- a]carbazole Natural Products.

Site-selective late-stage functionalizations of a pyrano[3,2- a]carbazole core related to the murrayamine natural products is reported. Specifically, selective C3 and C6 bromination has been achieved as well as C8 borylation. These functionalizations set the stage for access to a variety of natural products as well as their derivatives.