Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium-Ion Asymmetric Counteranion-Directed Catalysis
Trevor J. Seguin
Department of Chemistry, Texas A&M University, College Station, TX, 77842 USA
Search for more papers by this authorCorresponding Author
Prof. Steven E. Wheeler
Department of Chemistry, Texas A&M University, College Station, TX, 77842 USA
Search for more papers by this authorTrevor J. Seguin
Department of Chemistry, Texas A&M University, College Station, TX, 77842 USA
Search for more papers by this authorCorresponding Author
Prof. Steven E. Wheeler
Department of Chemistry, Texas A&M University, College Station, TX, 77842 USA
Search for more papers by this authorGraphical Abstract
Catalysis conundrum cracked computationally: The enantioselectivity of asymmetric Lewis acid organocatalysis of the Diels–Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state.
Abstract
Computational analysis shows that the enantioselectivity of asymmetric Lewis-acid organocatalysis of the Diels–Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state. These results not only explain the stereoselectivity of these silylium-ion-ACDC reactions but should also guide the development of more effective ion-pairing asymmetric organocatalysts.
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