Novel Three-Component Coupling Using Aluminum Tris(2,6-diphenylphenoxide) (ATPH): The Same Synthetic Strategy Leads to trans- and cis-Jasmonates

Abstract

A one‐pot three‐component coupling involving organolithium reagents, ATPH⋅cyclopentenone complex, and dihydrofuran⋅BCl3 complex (see scheme) gives moderate to good yields of the products with selective formation of either the 2,3‐cis or 2,3‐trans isomer, depending on the nature of the lithium reagent.

Synthesis and structure of aluminium amine-phenolate complexes

“…Treatment of ligand L 1 H 3 with one equivalent of [Al(O i Pr) 3 ] in toluene under ambient conditions yields the colourless adduct complex [HO i Pr·Al(L 1 )], whereas, a similar reaction of ligand L 1 H 3 with [Al(O i Pr) 3 ] in THF yields the colourless adduct [THF·Al(L 1 )] (Scheme 2), which has previously been reported by Verkade 42 from the reaction of the dimer, [Al(L 1 )] 2 , with THF, although the molecular structure of the complex has not been reported. The complex [THF·Al(L 1 )] has also been formed by the reaction of L 1 H 3 with AlMe 3 in THF.…”

“…Solvents were purified by conventional procedures and distilled prior to use. AlMe 3 and Al(O i Pr) 3 were purchased from Aldrich and used as received, without further purification. Solution 1 H, and 13 C NMR experiments were performed at ambient temperature (unless otherwise stated) using Bruker Avance-300 and Avance-400 MHz FT-NMR spectrometers.…”

“…Solution 1 H, and 13 C NMR experiments were performed at ambient temperature (unless otherwise stated) using Bruker Avance-300 and Avance-400 MHz FT-NMR spectrometers. 1 3 (2 mmol, 0.41 g) in toluene (10 ml) was added dropwise by syringe, at ambient temperature. The reaction mixture was allowed to stir for 2 h. The solvent was removed under reduced pressure.…”

Multicomponent Reactions in the Total Synthesis of Natural Products

“…The jasmonates are another class of disubstituted cyclopentanoid natural products very reminiscent of the prostaglandins. To efficiently assemble their main skeleton, Yamamoto and co-workers developed a clever three-component reaction methodology that was demonstrated by the total synthesis of both trans-and cismethyl jasmonates 36 and 37 (Scheme 12.7) [25].…”

“…Synthesis of jasmonates using a Noyori-type 3CR, by Yamamoto and co-workers [25]. ATPH ¼ aluminum tris(2,6-diphenylphenoxide), DMAP ¼ 4-dimethylaminopyridine, THF ¼ tetrahydrofuran.…”