2023
DOI: 10.1002/anie.202300036
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Nickel‐Catalyzed Unsymmetrical Bis‐Allylation of Alkynes

Abstract: The catalytic bis-allylation of alkynes is an important but challenging protocol to construct all-carbon tetrasubstituted alkenes. Particularly, the catalytic unsymmetrical bis-allylation of alkynes remains as an underexplored task to date. We herein report an unprecedented unsymmetrical bis-allylation by simultaneously utilizing electrophilic trifluoromethyl alkene and nucleophilic allylboronate as the allylic reagents. With the aid of robust Ni 0 /NHC catalysis, valuable skipped trienes can be obtained in hi… Show more

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Cited by 16 publications
(16 citation statements)
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“…The Chen group described the nickel-catalyzed three-component bis-allylation of alkynes with trifluoromethyl alkenes and allylboronates as allylic sources, providing an efficient method for the synthesis of valuable skipped trienes 179 with excellent regio- and stereoselectivity (Scheme ). Mechanistic studies suggest that the reaction is initiated by the oxidative cyclometalation of alkyne, trifluoromethyl alkene, and Ni(0) to generate nickelacycle intermediate 180 . β-Fluorine elimination of intermediate 180 gives alkenylnickel intermediate 181 , which undergoes transmetalation with allylboronate to furnish nickel­(II) species 182 .…”
Section: Nickel-catalyzed Defluorinative Cross-coupling Of Trifluorom...mentioning
confidence: 99%
“…The Chen group described the nickel-catalyzed three-component bis-allylation of alkynes with trifluoromethyl alkenes and allylboronates as allylic sources, providing an efficient method for the synthesis of valuable skipped trienes 179 with excellent regio- and stereoselectivity (Scheme ). Mechanistic studies suggest that the reaction is initiated by the oxidative cyclometalation of alkyne, trifluoromethyl alkene, and Ni(0) to generate nickelacycle intermediate 180 . β-Fluorine elimination of intermediate 180 gives alkenylnickel intermediate 181 , which undergoes transmetalation with allylboronate to furnish nickel­(II) species 182 .…”
Section: Nickel-catalyzed Defluorinative Cross-coupling Of Trifluorom...mentioning
confidence: 99%
“…It shows that high electron density of the Fe─N 4 structure causes an excessively strong binding of the oxygen intermediates, which is caused by an upshifting of the d z2 metal orbital and an increase in the molecular hardness, or the distance between d z2 and the molecular oxygen energy level, but the asymmetric electronic density of the Fe─N 4 Vc structure optimizes the adsorption toward O 2 and the intermediates and thus lowers the energy barrier for ORR. [51] Figure 4d and Figure S34 (Supporting Information) display the Gibbs free energy profile of ORR catalysis steps on different structures at U = 0 V. Both the normal Fe─N 4 moieties and Fe─N 4 Vc structures showed a consistent downhill energy pathway, indicating a thermodynamically favorable process on their surfaces. At a potential of 1.23 V, however, the rate determination steps (RDS) of the Fe─N 4 and Fe─N 4 Vc structures presented an uphill free energy profile ascribed by the fourth electron transfer step (*OH + e − → OH − ).…”
Section: Catalytic Mechanisms Investigationmentioning
confidence: 99%
“…Like Koh, Gutierrez, and co-workers, two additional three-component methods were reported; however, instead of generating quaternary centers, these reactions produced difficult-to-access tetrasubstituted alkenes stereoselectively (Scheme ). The process designed by Wang, Zheng, and co-workers uses aryl boronic acids, aldehydes, and alkynes to produce allylic alcohols (Scheme A). Conditions were screened to avoid generating the reductive coupling and 1,2-addition products, resulting in excellent ( Z )-selectivity.…”
Section: Ni Catalysismentioning
confidence: 99%