Propellanes are a unique class of compounds currently consisting of well over 10 000 representatives, all featuring two more or less inverted tetrahedral carbon atoms that are common to three bridging rings. The central single bond between the two bridgeheads is significantly weakened in the smaller entities, which leads to unusual reactivities of these structurally interesting propeller-like molecules. This Review highlights the synthesis of such propellanes and their occurrence in material sciences, natural products, and medicinal chemistry. The conversion of [1.1.1]propellane into bridgehead derivatives of bicyclo[1.1.1]pentane, including oligomers and polymers with bicyclo[1.1.1]penta-1,3-diyl repeat units, is also featured. A selection of natural products with larger propellane subunits are discussed in detail. Heteropropellanes and inorganic propellanes are also addressed. The historical background is touched in brief to show the pioneering work of David Ginsburg, Günther Snatzke, Kenneth B. Wiberg, Günter Szeimies, and others.

Herein, we describe an extension of our previously reported photomediated disulfide rebridging methodology to the conjugation of peptides and proteins. The methodology proved to be reproducible with various alkynes and different peptides. This study includes the first rebridging of the disulfide bond of a peptide through a thiol-yne reaction with a cyclooctyne. In all cases, the rebridging was proven by MS analyses and confirmed by the absence of olefinic protons on (1)H NMR spectra of the resulting products. Finally, this one-pot reduction thiol-yne conjugation was successfully applied to an antibody Fab fragment with a promising conversion, which set a good ground for the future syntheses of new protein and antibody conjugates.

This comprehensive review covers the isolation of naturally [3.3.3]propellanes and total synthesis approaches towards this challenging core.

Herein, we report on the conjugation of trastuzumab with 2,5-difluorobenzene diazonium tetrafluoroborate.

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Propellane bilden eine einzigartige Verbindungsklasse, die derzeit aus deutlich mehr 10 000 Vertretern besteht, die alle zwei mehr oder weniger invertierte tetraedrische Kohlenstoffatome aufweisen, die drei Ringbrücken gemeinsam haben. Die zentrale Einfachbindung zwischen den beiden Brückenköpfen ist in den kleineren Gebilden deutlich geschwächt, was zu ungewöhnlichen Reaktivitäten dieser strukturell interessanten Propeller‐artigen Moleküle führt. Dieser Aufsatz soll die Synthesen solcher Propellane und ihr Auftreten in den Materialwissenschaften, Naturstoffen sowie der medizinischen Chemie hervorheben. Die Umwandlung von [1.1.1]Propellan zu Brückenkopfderivaten von Bicyclo[1.1.1]pentan einschließlich Oligomeren sowie Polymeren mit Bicyclo[1.1.1]penta‐1,3‐diyl‐Wiederholungseinheiten wird besonders herausgestellt. Eine Auswahl von Naturstoffen mit größeren Propellanuntereinheiten wird detailliert diskutiert. Außerdem werden Heteropropellane und anorganische Propellane angesprochen. Der historische Hintergrund wird kurz anhand der grundlegenden Arbeiten von David Ginsburg, Günther Snatzke, Kenneth B. Wiberg, Günter Szeimies und anderen angerissen.

The [2,3]-Wittig rearrangement of propargyloxy acetates bearing a propargylic stereocenter opposite to the oxyacetic acid moiety gives α-hydroxy-γ-amino acids containing an allene unit under high stereocontrol. The resulting product displays a novel type of γ-amino acid with a potentially intriguing biological profile.

Hexahydro -3-phenyl-6,7,8-trihydroxy-3R-[3α,5β,6β,7α,8β,8aβ]-5H-oxazolo[3,2-a]pyridine-5-carbonitrile is endowed with two non equivalent reactive sites: an α-amino nitrile at the C-5 position and an α-amino ether at the C-8a position. Herein, alkylation at the C-5 position was studied. The scope and limitations of these reactions have been investigated.