Green Hydroselenation of Aryl Alkynes: Divinyl Selenides as a Precursor of Resveratrol

Abstract

A simple and efficient protocol to prepare divinyl selenides has been developed by the regio- and stereoselective addition of sodium selenide species to aryl alkynes. The nucleophilic species was generates in situ, from the reaction of elemental selenium with NaBH4, utilizing PEG-400 as the solvent. Several divinyl selenides were obtained in moderate to excellent yields with selectivity for the (Z,Z)-isomer by a one-step procedure that was carried out at 60 °C in short reaction times. The methodology was extended to tellurium, giving the desired divinyl tellurides in good yields. Furthermore, the Fe-catalyzed cross-coupling reaction of bis(3,5-dimethoxystyryl) selenide 3f with (4-methoxyphenyl)magnesium bromide 5 afforded resveratrol trimethyl ether 6 in 57% yield.

Resveratrol: a review of plant sources, synthesis, stability, modification and food application

“…In 2017, Perin et al . developed a simple and efficient protocol to prepare divinyl selenides through regio‐ and stereoselective addition of sodium selenide species to aryl alkynes in the presence of PEG‐400 as solvent . Another work reported a one‐step procedure at 60 °C with short reaction times, and obtained several divinyl selenides in moderate to excellent yields with selectivity for the ( Z,Z )‐isomer.…”

(Z,Z)-Selanediylbis(2-propenamides): Novel Class of Organoselenium Compounds with High Glutathione Peroxidase-Like Activity. Regio- and Stereoselective Reaction of Sodium Selenide with 3-Trimethylsilyl-2-propynamides

“…Vinyl selenides are important intermediates for organic synthesis [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 ]. These compounds have been used for the preparation of a number of valuable products [ 4 , 5 , 6 , 7 , 8 , 9 ]. Vinyl selenides have found application in the synthesis of functionalized ketones, ( Z )-allyl alcohols, and unsaturated aldehydes [ 4 ].…”

“…The coupling reaction of vinyl selenides with Grignard reagents provided corresponding functionalized alkenes [ 6 , 7 ]. The synthesis of resveratrol and its methoxylated analogues—well known compounds due to their anti-inflammatory, anticancer, antibacterial, and neuroprotective activity, has been proposed based on vinyl selenides [ 8 ]. An efficient method for preparation of α-phenylselanyl lactones has been developed from α-(phenylseleno)vinyl tozylates [ 9 ].…”

“…The main methods for the preparation of vinyl selenides include a transition metal catalyzed coupling of vinyl halides with diselenides or selenols [ 13 , 14 , 15 , 16 ], reactions of thiols or chalcogenolates with selenoalkynes [ 14 , 17 , 18 ], and addition of selenium-centered nucleophiles to acetylenes [ 8 , 14 , 19 , 20 , 21 , 22 , 23 ].…”

Celebrating Two Centuries of Research in Selenium Chemistry: State of the Art and New Prospective

“…The synthesis was carried out by two-component cyclization of the selenoureas and α-haloketones and the selenoureas were obtained from the reaction of Woollins’ reagent with cyanamides, followed by hydrolysis [ 3 ]. Other contributions pay attention to the ecofriendly aspect of synthesis, such as the paper from Braga et al [ 4 ] that described an efficient copper-catalyzed synthesis of unsymmetrical disubstituted chalcogenides using ligand- and solvent-free conditions; our manuscript, in which the use of novel zinc selenates was proposed for the preparation in “on-water” conditions of selenol esters [ 5 ]; and the efforts of Lenardao’s and Perin’s groups who suggested the use of glycerol as ecofriendly raw material in the synthesis of organoselanyl and organotellanyl alkynes [ 6 ] or the green hydroselenation of aryl alkynes to afford divinyl selenides as precursor in the synthesis of resveratrol [ 7 ]. The preparation of novel organoselenium compound having biological activity is here approached by Scianowski’s group with the synthesis of new cytotoxic Ebselen-like derivatives [ 8 ] as well as by Giurg and coworkers who prepared different derivatives of bis[(2-chlorocarbonyl)phenyl] diselenide demonstrating their antibacterial, antifungal and antiviral properties [ 9 ].…”