111-80-8Relevant articles and documents
Electrochemical selective incorporation of CO2 into terminal alkynes and diynes
Ko?ster, Frank,Dinjus, Erkhardt,Din?ach, Elisabet
, p. 2507 - 2511 (2001)
Electrochemical incorporation of CO2 into terminal alkynes and diynes on silver cathodes occurred selectively, to afford monocarboxylic acid derivatives in good yields. The electrolyses were carried out in one-compartment cells fitted with magnesium anodes, under mild conditions.
Understanding the mechanism of transition metal-free: Anti addition to alkynes: The selenoboration case
García-López, Diego,Civit, Marc G.,Vogels, Christopher M.,Ricart, Josep M.,Westcott, Stephen A.,Fernández, Elena,Carbó, Jorge J.
, p. 3617 - 3628 (2018/07/29)
The stereoselective anti-addition of selenoboranes to α,β-acetylenic esters and amides was achieved in a transition metal-free context using catalytic amounts of PCy3. The reaction provides anti-3,4-selenoboration with concomitant delivery of α-vinyl selenides by protodeboronation with MeOH. Interestingly, in the absence of phosphine the selenoboration switches towards the formation of β-vinyl selenides. Theoretical calculations rationalize the regio- and stereoselectivity of the reaction by discovering a new mechanism for the anti-3,4-selenoboration. While the selenoborane is activated via the "push-pull" effect of B, the phosphine interacts with the β position of the alkynoate switching the polarity of the triple bond and favoring 1,3-selenoboration which provides the α-addition of the selenyl group. Then, the autocatalytic action of a second selenoborane reagent, which coordinates to the phosphorus ylide intermediate, determines the stereoselectivity and completes the catalytic process. Finally, the comparison of selenoborane reagents with diboranes and silaboranes, which have exhibited analogous reactivity, shows that the selenium moiety has a larger nucleophilic character favoring the performance of the reaction under mild conditions.
CuI/Pd0 cooperative dual catalysis: Tunable stereoselective construction of tetra-substituted alkenes
Vercruysse, Sebastien,Cornelissen, Loic,Nahra, Fady,Collard, Laurent,Riant, Olivier
supporting information, p. 1834 - 1838 (2014/03/21)
This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a CuI/Pd0 cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways.
