Intramolecular [4 + 2] cycloaddition reactions of substituted 1,2-cyclohexadienes with pendent furans enables the synthesis of complex tetracyclic scaffolds in a single step under mild conditions. All Diels–Alder cycloadducts were obtained as single diastereomers, assigned as the endo isomer. Substrates were easily assembled via Stork–Danheiser alkylation of 3-ethoxy-2-bromocyclohex-2-enone to accommodate a range of tethers and furan traps. Cleavage of enol acetate moieties resulted in room-temperature Diels–Alder cycloreversion to tethered furyl cyclohexenones.

The tertiary amide is a ubiquitous functional group and plays an irreplaceable role in medicinal chemistry. Its robust nature has meantin the pastthat selective manipulation of this motif remained elusive. The reductive activation through hydrosilylation of tertiary amidesusing Vaska’s complex (IrCl­(CO)­(PPh3)2)has emerged as a powerful strategy for the chemoselective transformation of amides into reactive enamines and iminium ions. Furthermore, these synthetically valuable species can be accessed in the presence of traditionally more reactive functional groups. This approach to amide reductive activation via hydrosilylation has been exploited in a range of downstream C–C bond forming processes and has seen significant applications in total synthesis, enabling streamlined routes for the synthesis of complex natural product architectures. This perspective covers the development of this synthetic strategy, from initial hydrosilylation studies to its flourishing use in the reductive functionalization of amide-containing molecules, both simple and complex.

1,2-Cycloheptadiene is a strained, transient species that has been underutilized as a synthetic building block. Sevenmembered cyclic allenes are mostly known for their propensity to undergo rapid dimerization, and relatively little has been reported regarding their cycloaddition reactivity with 1,3-dienes or 1,3-dipoles. This work describes the trapping of 1-acetoxy-1,2cycloheptadiene and its unsubstituted counterpart, generated via desilylative elimination, with a range of 1,3-dipolar trapping partners, affording complex polycyclic products with high regio-and diastereoselectivity.