This paper describes a total synthesis of the terpene-derived natural product aritasone via the hetero-Diels–Alder [4 + 2] cyclodimerisation of pinocarvove, which represents the proposed biosyntheic route. The hetero-Diels–Alder dimerisation of pinocarvone did not proceed under standard conditions, and ultra-high pressure (19.9 kbar) was required. As it seems unlikely that these ultra-high pressures are accessible within a plant cell, we suggest that the original biosynthetic hypothesis be reconsidered, and alternatives are discussed.

Triazole-linked morpholino (TLMO) oligonucleic acids were synthesised using the CuI catalysed (3 + 2) azide–alkyne cycloaddition (CuAAC) reaction. The modified DNA analogues were incorporated into 13-mer sequences via solid phase synthesis. UV melting experiments showed that the TLMO modification gives higher Tm values than the corresponding TLDNA modification.

The copper-catalysed oxidative coupling of amines and H-phosphonates to produce phosphoramidates has been achieved using CuI as the catalyst and O2 (present in air) as the sole oxidant.

A computational study (B3LYP), of the metallation of a bridged ketone, an important step in the synthesis of a polycyclic polyprenylated acylphloroglucinol (PPAP), nemorosone, shows three energetically distinct structural possibilities for the lithiated intermediate. These findings, along with observations of the reactivity of the intermediates in bridgehead substitutions, suggest that different intermediates may be formed depending upon the type of process used for lithiation.

A formal synthesis of (+)-lactacystin has been completed from trans-4-hydroxyproline, using a diastereoselective enolate acylation reaction as a key step. Diastereoselectivity was seen to vary as a function of the steric bulk of the C4-O-protecting group, and contrary to expectations, the best diastereoselectivities were obtained when the small methyl carbonate protecting group was used. The formal synthesis was then completed by intercepting Shibasaki’s route via methyl carbonate deprotection, dehydration, 3-pyrroline to 3-pyrrolinone oxidation, hydrogenation and N-CO2Me deprotection.

Treating readily available α-diazo-β-ketoesters with HBF4 results in nucleophilic fluorination by the usually inert and stable tetrafluoroborate anion. The resulting α-fluoro-β-ketoesters are highly versatile synthetic intermediates, for example in the preparation of fluoro-heterocycles, as illustrated by the direct formation of fluoro-pyrimidines, -pyrazoles and -coumarins in a single step.

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under potentially prebiotic conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (L)-proline yield (L)-tetroses, esters of (L)-leucine, (L)-alanine and (L)-valine generate (D)-tetroses, offering the potential to account for the link between natural (L)-amino acids and natural (D)-sugars. The effect of pH and NaCl on the yields and enantioselectivities was also investigated and was shown to be significant, with the optimal enantioselectivities occurring at pH 7.

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under aqueous conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (L)-proline yield (L)-carbohydrates, esters of (L)-leucine and (L)-alanine generate (D)-carbohydrates, offering the potential to account for the prebiotic link between natural (L)-amino acids and natural (D)-sugars.

The tricyclic spirochroman core of dihypoestoxide has been synthesized from geranoic acid in seven steps using a hetero-Diels−Alder cycloaddition as a key step, thus providing support for the proposed biosynthesis of the natural product. Furthermore, analysis of the 13C NMR data obtained for all four diastereoisomers of the synthetic spirochroman core has allowed us to propose a full stereochemical assignment for dihypoestoxide.

A range of electrophilic ethers were prepared via DDQ oxidation and alcoholic trapping (propanol, crotyl alcohol and propargyl alcohol) at the C4 position of (+)-catechin. The Lewis acid-mediated C4-substitution of each of these ethers was examined and it was found that the propargyl ether was the best overall electrophile. A range of Lewis acids were then examined as activators and it was found that BF3·OEt2 was the best in terms of both yield and stereochemical control at the C4 position. This newly developed set of conditions was then used to prepare the natural product nutraceutical procyanidin B3 with complete control of stereochemistry.

We have developed an in-flow process for the synthesis of β-keto esters via the BF3·OEt2-catalyzed formal C−H insertion of ethyl diazoacetate into aldehydes. The β-keto esters were then condensed with a range of amidines to give a variety of 2,6-substituted pyrimidin-4-ols.

A total synthesis of (+)-cymbodiacetal (1) has been completed from (R)-(+)-limonene oxide using a hetero-Diels−Alder cycloaddition as a key step. The key Diels−Alder cycloaddition proceeds with endo-selectivity (2:1, endo/exo) in quantitative yield, and the two diastereomeric spirochroman products are isolable, stable products. Furthermore, the exo- and the endo-hetero-Diels−Alder cycloaddition products (2 and 7) can be oxidized with m-CPBA to produce (+)-cymbodiacetal (1) and the C2-symmetric bis-hemiacetal structure 8, respectively. The isomeric hemiacetal 9 is produced in both oxidation reactions. The structures of (+)-cymbodiacetal (1), its C2-symmetric diastereoisomer 8, and the isomeric hemiacetal 9 were confirmed using X-ray crystallography.

Rhodium(II) catalysts and PhIO in benzene convert homoallylic carbamates into the corresponding aziridines at room temperature.

Triazole-linked morpholino (TLMO) oligonucleic acids were synthesised using the CuI catalysed (3 + 2) azide–alkyne cycloaddition (CuAAC) reaction. The modified DNA analogues were incorporated into 13-mer sequences via solid phase synthesis. UV melting experiments showed that the TLMO modification gives higher Tm values than the corresponding TLDNA modification.

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under potentially prebiotic conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (L)-proline yield (L)-tetroses, esters of (L)-leucine, (L)-alanine and (L)-valine generate (D)-tetroses, offering the potential to account for the link between natural (L)-amino acids and natural (D)-sugars. The effect of pH and NaCl on the yields and enantioselectivities was also investigated and was shown to be significant, with the optimal enantioselectivities occurring at pH 7.

A computational study (B3LYP), of the metallation of a bridged ketone, an important step in the synthesis of a polycyclic polyprenylated acylphloroglucinol (PPAP), nemorosone, shows three energetically distinct structural possibilities for the lithiated intermediate. These findings, along with observations of the reactivity of the intermediates in bridgehead substitutions, suggest that different intermediates may be formed depending upon the type of process used for lithiation.

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under aqueous conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (L)-proline yield (L)-carbohydrates, esters of (L)-leucine and (L)-alanine generate (D)-carbohydrates, offering the potential to account for the prebiotic link between natural (L)-amino acids and natural (D)-sugars.

Treating readily available α-diazo-β-ketoesters with HBF4 results in nucleophilic fluorination by the usually inert and stable tetrafluoroborate anion. The resulting α-fluoro-β-ketoesters are highly versatile synthetic intermediates, for example in the preparation of fluoro-heterocycles, as illustrated by the direct formation of fluoro-pyrimidines, -pyrazoles and -coumarins in a single step.

The copper-catalysed oxidative coupling of amines and H-phosphonates to produce phosphoramidates has been achieved using CuI as the catalyst and O2 (present in air) as the sole oxidant.