Appel reaction conditions have been harnessed to affect a mild biosynthetically inspired dehydration of endoperoxides to deliver multi-substituted electron rich furans. Unlike traditional dehydrative procedures, this method is metal and acid free, and can be achieved under redox neutral conditions. It is general for a range of aryl and alkyl substituted endoperoxides, and is functional group tolerant. Furthermore, this procedure has been used to deliver an effective total synthesis of the furan fatty acid (FFA) F5.

We report a facile method for the synthesis of 1,3-dienes by a sequential process consisting of a palladium-catalyzed, base-free, Suzuki–Miyaura coupling/isomerization sequence. This sequence couples boronic acids with propargyl alcohols, generating the requisite allene in situ, followed by conversion of the unactivated allene to its 1,3-diene via a hydro-palladation/dehydro-palladation process. This process is general for a range of boronic acids, including boronic acids with electron-donating and -withdrawing groups, as well as heteroarylboronic acids. Key to this process is the boric acid byproduct of the base-free Suzuki–Miyauru coupling, which generates the required palladium–hydrido complex [H–PdII–OB(OH)2] required for the isomerization.

By way of appending the C2-symmetric carbocyclic cleft diol with thiocarbamates with varying substituents, significant control of the hydrogen bonded network can be achieved. Smaller alkyl substituents lead to the formation of stacked columns of components with the apex of one molecule suitably aligned in the cleft of a second. Aryl substituents, however, lead to the formation of ribbons via an H-bonding network. Additionally, the packing of these ribbons into networks is considerably different between the enantiopure and racemic clefts, with the latter giving rise to channels within the crystal structure.

Pyridyl-assisted templating of phenyl boronic acid has been utilised to link two remote boroxines via a chiral spacer. The chiral spacer is a carbocyclic analogue of Tröger’s base and contains a unique chiral cavity, and the flanking boroxine units have been shown, by single crystal X-ray analysis, to extend the size and shape of this cavity.

A one-pot transformation of amides, ureas, carbamates and sulfonamides into synthetically useful N-allenyl analogues using a tBuOK/DMSO protocol is reported. The procedure is experimentally simple and robust, and provides N-allenyl analogues, commonly used within the literature, in yields comparable to the benchmark two-step approach.

Au(I) activation of allenamides in the presence of phenols leads to the formation of chromanes in moderate to good yields. This catalytic process is dependent on the counterion which facilitates the activation of the in situ formed imine. Furthermore, this iminium can be intercepted by trimethylallyl silane, via the Hosomi–Sakurai reaction, giving a formal procedure for the regioselective intermolecular addition of two carbon nucleophiles to an allenamide at the α- and γ-positions.

Treatment of bicyclo[2.2.2]oct-2-en-7-one with organometallic reagents gives the addition products in good yield and moderate diastereoselectivities in favour of the syn-products. Subsequent exposure of these addition products to ruthenium catalysed ring rearrangement metathesis (RRM) conditions reveals significant product divergence as a consequence of the newly acquired stereocentre.

The intermolecular addition of 1,3-dicarbonyl equivalents to endoperoxides in the presence of an organocatalyst yields trans-fused butyrolactones in high yield and enantioselectivities. This methodology expands the synthetic utility of endoperoxides and further underlines their potential as sources of oxygen functionality for natural and non-natural product target synthesis.

The addition of allyl magnesium and allyl indium reagents to a key TBS protected norbornenyl building block, synthesised in 6-steps from commercially available 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, has been achieved providing the syn addition products with high diastereoselectivity. The subsequent exposure of the addition products to metathesis conditions, in the presence of ethene, then provided cis fused[3.0.3]-carbocycles with very high regioselectivity, via a Ring Rearrangement Metathesis (RRM) transformation.

A mild and facile synthesis of enamides has been developed, based on nucleophilic addition of electron-rich aromatic and heteroaromatics to an allenamide unit catalyzed by a gold salt. Yields for the transformation were 29−98%.

Appel reaction conditions have been harnessed to affect a mild biosynthetically inspired dehydration of endoperoxides to deliver multi-substituted electron rich furans. Unlike traditional dehydrative procedures, this method is metal and acid free, and can be achieved under redox neutral conditions. It is general for a range of aryl and alkyl substituted endoperoxides, and is functional group tolerant. Furthermore, this procedure has been used to deliver an effective total synthesis of the furan fatty acid (FFA) F5.

The addition of allyl magnesium and allyl indium reagents to a key TBS protected norbornenyl building block, synthesised in 6-steps from commercially available 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, has been achieved providing the syn addition products with high diastereoselectivity. The subsequent exposure of the addition products to metathesis conditions, in the presence of ethene, then provided cis fused[3.0.3]-carbocycles with very high regioselectivity, via a Ring Rearrangement Metathesis (RRM) transformation.