Total synthesis of solanoeclepin A

Abstract

Cyst nematodes are troublesome parasites that live on, and destroy, a range of important host vegetable plants. Damage caused by the potato cyst nematode has now been reported in over 50 countries. One approach to eliminating the problem is to stimulate early hatching of the nematodes, but key hatching stimuli are not naturally available in sufficient quantities to do so. Here, we report the first chemical synthesis of solanoeclepin A, the key hatch-stimulating substance for potato cyst nematode. The crucial steps in our synthesis are an intramolecular cyclization reaction for construction of the highly strained tricyclo[5.2.1.0¹'⁶]decane skeleton (DEF ring system) and an intramolecular Diels-Alder reaction of a furan derivative for the synthesis of the ABC carbon framework. The present synthesis has the potential to contribute to addressing one of the critical food issues of the twenty-first century.

An oxazetidine amino acid for chemical protein synthesis by rapid, serine-forming ligations

“…We reasoned that if a hydroxylamine-epoxide ( Fig. 1b) underwent an intramolecular cyclization, it could potentially give the oxazetidine by a 4-exo-tet pathway rather than the disfavoured 5-endo-tet closure 15,16 , as a similar strategy has proven successful for cyclobutane formation 17 . A carbamate-protected hydroxylamine 2 ( Fig.…”

Intramolecular [2+2] Cycloaddition of Homoallylketenes to Bicyclo[2.1.1]hexan-5-ones

“…17,18) These compounds have been prepared by photolysis of γ,δ-unsaturated chromium-carbene complexes, 10) intramolecular alkylation of 2-tosyloxymethylcyclopentanones 19,20) and β′-silyloxy enol triflate, 21) or oxidative rearrangement of bicyclo[2.2.0]hexan-2-ol.…”

Discovery of Novel Synthetic Methodologies and Reagents during Natural Product Synthesis in the Post-Palytoxin Era

“…Within recent years, the increased focus on the extermination of PCNs has been aimed at application of the hatch stimulus solanoeclepin A, which has subsequently attracted significant attention in the synthetic community. 249 During their studies aimed at construction of the sevenmembered ring system (Scheme 59), Sarpong and coworkers 250 The optimized reaction conditions developed by Sarpong and co-workers 250 enabled the synthesis of a series of enals, enones, and dienones that are otherwise difficult to access from simple divinyl and enyne carbinols in a palladium-mediated anomalous Heck reaction (Scheme 61).…”