The stereoselective total synthesis of (+)-garvensintriol

A simple and highly efficient stereoselective total synthesis of (+)-garvensintriol, isolated from the stem bark of Goniothalamus arvensis, is described using Sharpless kinetic resolution, MacMillan α-hydroxylation, and Horner-Wadsworth-Emmons olefination as the key steps.     

Synthesis of (R)‐Japonilure and (4R,9Z)‐9‐Octadecen‐4‐olide,Pheromones of the Japanese Beetle and Currant Stem Girdler

Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)‐japonilure (1) and (4R,9Z)‐9‐octadecen‐4‐olide (2), has been achieved.     

Oxidation of BINOLs by Hypervalent Iodine Reagents: Facile Synthesis of Xanthenes and Lactones

Xanthene derivatives have broad applications in medicines, fluorescent probes, dyes, food additives, etc. Therefore, much attention was focused on developing the synthetic methods to prepare these compounds. Binaphthyl-based xanthene derivatives were prepared through the oxidation of BINOLs promoted by the hypervalent iodine reagent iodosylbenzene (PhIO). Nine-membered lactones were obtained through a similar oxidative reaction when iodoxybenzene (PhIO₂) was used. Additionally, one-pot reactions of BINOLs, PhIO and nucleophiles such as alcohols and amines were also investigated to provide alkoxylated products and amides in good to excellent yields.     

Synthesis of a new class of bisheterocycles via the Heck reaction of eudesmane type methylene lactones with 8-bromoxanthines

The eudesmane-type methylene lactones (isoalantolactone, alantolactone, 4,15-epoxyisoalantolactone, 2′,2′-dichloro-4H-spiro[cyclopropane-1′,4-eudesma-11(13)-en-8β,12-olide], and alantolactone) react with 8-bromoxanthines (8-bromocaffeine, 8-bromotheobromine, 8-bromo-3-butyltheobromine, 8-bromotheophylline, 8-bromo-9-butyltheophylline) under Heck reaction conditions to produce the target (E)-13-(2,6-dioxo-2,3-dihydro-1H-purin-8-yl)eudesma-4(15),11(13)-dien-8β,12-olides and the subsequent endocyclic isomers - 11-(2,6-dioxo-2,3-dihydro-1H-purin-8-yl)-13-normethyleudecma-4(15)-7(11)-dien-8α,12-olides. It was revealed that the yield and product ratio depends on the reaction conditions and the structure of methylene lactone. The effectiveness of Pd(OAc)₂–caffeine catalytic system has been demonstrated in this reaction. The electric eel acetylcholinesterase inhibitory activity of the eudecmanolide-xanthine hybrids was evaluated. Among the new type bisheterocycles compound 27 with butyl and 2-oxodecahydronaphtho[2,3-b]furan-3(2H)-ylidene)methyl substituents at C-7 and C-8 of the xanthine core showed moderate activity with IC₅₀ value of 40 μM.     

Simple Synthesis of Versatile Coumarin Scaffolds

We describe an approach using ring‐closing metathesis (RCM) to synthesize versatile coumarin derivatives that present appropriate substitutions both at the aromatic and at the α,β‐unsaturated lactone ring. The obtained compounds can be used as molecular scaffolds suitable for further diversifications through a combinatorial approach.     

Double Asymmetric Induction in 1,3‐Dipolar Cycloaddition of Nitrones to 2,3‐Unsaturated Sugar 1,5‐Lactones

1,3‐Dipolar cycloaddition of nitrones 1–3 to the α,β‐unsaturated δ‐lactones, non‐chiral 4, d‐glycero 5, dl‐glycero 5/5ent, d‐erythro 6, and d‐threo 7, provides an interesting example of a double asymmetric induction. In all cases, only the exo approach of reactants was observed. The high preference of anti addition of the nitrones to the terminal acetoxymethyl group in the lactones 5–7 is consistent with previous observations, and can be explained in terms of the axial approach of the nitrone oxygen atom. The 3‐t‐butoxy group of the nitrone plays a similar role. In the case of mismatched pairs, the location of the 4‐acetoxy substituent in the lactone and that of the 4‐t‐butoxy one in the nitrone become decisive for the outcome of the addition. CD‐spectroscopy proved to be an attractive tool to determine the absolute configuration of the cycloadducts.     

Radical Cyclization Route to the Stereoselective Synthesis of (+)‐trans‐Cognac Lactone and (+)‐trans‐Aerangis Lactone

Stereoselective total synthesis of two chiral lactones, (+)‐trans‐cognac lactone (1b) and (+)‐trans‐aerangis lactone (2c), has been achieved from the same intermediate using a radical‐based cyclization route.     

Two distinct pathways for essential metabolic precursors for isoprenoid biosynthesis

Isoprenoids are a diverse group of molecules found in all organisms, where they perform such important biological functions as hormone signaling (e.g., steroids) in mammals, antioxidation (e.g., carotenoids) in plants, electron transport (e.g., ubiquinone), and cell wall biosynthesis intermediates in bacteria. All isoprenoids are synthesized by the consecutive condensation of the five-carbon monomer isopentenyl diphosphate (IPP) to its isomer, dimethylallyl diphosphate (DMAPP). The biosynthetic pathway for the formation of IPP from acetyl-CoA (i.e., the mevalonate pathway) had been established mainly in mice and the budding yeast Saccharomyces cerevisiae. Curiously, most prokaryotic microorganisms lack homologs of the genes in the mevalonate pathway, even though IPP and DMAPP are essential for isoprenoid biosynthesis in bacteria. This observation provided an impetus to search for an alternative pathway to synthesize IPP and DMAPP, ultimately leading to the discovery of the mevalonate-independent 2-C-methyl-D-erythritol 4-phosphate pathway. This review article focuses on our significant contributions to a comprehensive understanding of the biosynthesis of IPP and DMAPP.