Highly stereoselective synthesis of trisubstituted olefins via addition of alkylcopper complexes to acetylenes

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

“…A variety of substrates were used in this reaction to establish the generality and efficiency, and all reactions proceeded smoothly under similar conditions. The experimental results showed that the present method was effective for substrates possessing either aryl groups (Table 1, entries [2][3][4][5][6][7][8][9][10] or alkyl ones (Table 1, entries 11 and 12). Among substrates bearing aryl groups, those containing electron-withdrawing functionalities reacted more slowly and gave slightly reduced yields of products (Table 1, entry 9).…”

“…The biological properties of these alkenes are highly dependent on the configuration of the C C bonds [2]. Therefore, a number of methods have been developed for the stereoselective synthesis of trisubstituted alkenes [2,3].…”

“…The biological properties of these alkenes are highly dependent on the configuration of the C C bonds [2]. Therefore, a number of methods have been developed for the stereoselective synthesis of trisubstituted alkenes [2,3]. In view of their significance in organic synthesis and potential bioactivity, it is still desirable to extend the scope of trisubstituted alkene family and develop new and convenient synthetic routes.…”

Synthetic Applications of the Baylis–Hillman Reaction: Simple and Convenient Synthesis of Five Important Insect Pheromones

“…-Trisubstituted alkene moieties have been widely observed in several natural bioactive compounds including different pheromones and antibiotics [1]. The biological properties of these alkenes are remarkably dependent on the configuration of the C=C bond [2]. A number of methods have been developed for the stereoselective synthesis of trisubstituted alkenes [2 -6].…”

“…[24]. To overcome this problem, we followed the recently reported protocol for the asymmetric Baylis-Hillman reaction of a-branched chiral aldehydes in presence of 50 mol-% of DABCO in CH 2 [25]. With this protocol, we achieved a 51% yield of adduct 4, isolated as an inseparable mixture of two diastereoisomers after 22 h. To enhance the yield of 4 without impairing the optical activity, we made several attempts to synthesize 4 within shorter time, based on methods published in a thorough literature survey [14b].…”