First application of attractive intramolecular interactions to the design of chiral catalysts for highly enantioselective Diels-Alder reactions

Corey, E. J.; Loh, Teck Peng

doi:10.1021/ja00023a066

Cited by 267 publications

(115 citation statements)

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“…It also emerges that optimization of the B97 functional with empirical dispersion corrections leads to essentially zero dispersion correction. The Diels-Alder reaction (DA) has a well-known secondary orbital interaction between the diene and the dienophile, which can influence the reaction [14]. The addition of dienophiles to dienes can proceed via a concerted mechanism, meaning that the two new CC bonds form "in concert" rather than sequentially.…”

Section: Introductionmentioning

confidence: 99%

Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier

Liang

Liu

et al. 2018

Journal of Chemistry

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The interactions (including weak interactions) between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to investigate different substituent groups incorporated on the dienophiles and dienes. The bond order is used to track the trajectory of the cycloaddition reaction. The deformation/interaction model is used to obtain the interaction energy from the reactant complex to the inflection point until reaching the saddle point. The interaction energy initially increases with a decrease in the interatomic distance, reaching a maximum value, but then decreases when the dienophiles and dienes come closer. Reduced density gradient and chemical energy component analysis are used to analyse the interaction. Traditional transition state theory and variational transition state theory are used to obtain the reaction rates. The influence of tunneling on the reaction rate is also discussed.

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Section: Introductionmentioning

confidence: 99%

Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier

Liang

Liu

et al. 2018

Journal of Chemistry

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“…99.5 % ee) in 94 % yield (exo/endo 96:4, Scheme 2). [14] Later Corey et al showed that protonated oxazaborolidinium triflates such as 5 have an extraordinarily broad application profile as catalysts in enantioselective DielsAlder reactions. For example, the cycloaddition of 2-methyl-1,3-butadiene (6) with 2-methylpropenal (7) at À78 8C affords 8 in 96 % yield and 97 % ee (Scheme 3).…”

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confidence: 99%

Oxazaborolidines as Catalysts for Enantioselective Cycloadditions: Now [2+2]!

Butenschön

2008

Angew Chem Int Ed

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“…Diene 9 proved to be unstable towards the Keck and Mikami catalysts, even at À78 8C. Use of the Corey (S)-tryptophan-derived oxazaborolidine [10] (C) failed to give selectivities with diene 8 and 9 (entries 4 and 5). Diene 7 did not react in the presence of C, and was recovered from the reaction.…”

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confidence: 99%

“…[a] A = Keck catalyst; [8] B = Mikami catalyst; [9] C = Corey catalyst derived from (S)-tryptophan; [10] D = MacMillan imidazolidinone; [11] [b] Bz = benzoyl, PMB = para-methoxybenzyl, TBS = tert-butyldimethylsilyl; [6b]…”

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confidence: 99%