Origins of Regioselectivity of Diels−Alder Reactions for the Synthesis of Bisanthraquinone Antibiotic BE-43472B

Hayden, Amy E.; Paton, Robert S.; Becker, Jochen; Lim, Yee Hwee; Nicolaou, K. C.; Houk, K. N.

doi:10.1021/jo902572y

Cited by 17 publications

(6 citation statements)

References 25 publications

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“…On the basis of the above results as well as other reports, a plausible reaction mechanism is depicted in Scheme . According to the dual activation model, the two substrates involved in the reaction are activated simultaneously by the bifunctional catalyst.…”

Section: Methodssupporting

confidence: 74%

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Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions

et al. 2020

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An efficient enantioselective construction of tetrahydronaphthalene-1,4-diones as well as dihydronaphthalene-1,4-diols by a chiral phosphoric acid catalyzed quinone Diels-Alder reaction with dienecarbamates is reported. The nature of the protecting group on the diene is key to the success of achieving high enantioselectivity. The divergent "redox" selectivity is controlled by using an adequate amount of quinones. Reversible redox switching without erosion of enantioselectivity was possible from individual redox isomers.

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Section: Methodssupporting

confidence: 74%

“…Relatively few mechanistic studies on quinones centered [4+2] cycloaddition have been conducted, but a concerted mechanism rather than a stepwise mechanism has been often suggested. However, based on a recent theoretical study, a stepwise ionic mechanism has been proposed .…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions

et al. 2020

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“…We provide the whole potential energy profile of the tandem cycloaddition process in Figure and various conformers of species with small differences in energy in Figures S1–S4 (Supporting Information). The general mechanism shows that the first step of the cascade reaction corresponding to the D–A cycloaddition proceeds via the transition state TS1 with an activation free energy of 27.1 kcal/mol in a concerted but significantly asynchronous fashion, and both the diene and dienophile appear to be symmetrical. , The formation of the D–A adduct 3 is exergonic by 4.8 kcal/mol. The subsequent step is intramolecular [2 + 2 + 2] cycloaddition with an activation free energy of 29.9 kcal/mol in water (30.0 kcal/mol in MeCN).…”

Section: Resultsmentioning

confidence: 99%

DFT and Experimental Exploration of Intramolecular [2 + 2 + 2] Cycloaddition of Oxanorbornadienedicarboxylates and Analogues

2013

J. Org. Chem.

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The facile intramolecular [2 + 2 + 2] homo-Diels-Alder cycloadditions of oxanorbornadienedicarboxylates and analogues have been investigated by theoretical calculations using B3LYP and M06-2X density functional methods and experimental confirmation. The oxanorbornadienedicarboxylates formed from furans and but-2-ynedioates undergo the resulting intramolecular [2 + 2 + 2] cycloaddition in a concerted but asynchronous fashion, requiring energy barriers of about 30 kcal/mol to construct five- and three-membered rings simultaneously. Bridgehead substitutents have little influence on the regioselectivity, whereas 5-substitutents involving steric hindrance or electron-acceptor groups are predicted to attenuate the cycloaddition at the substituted side. Furthermore, the linker length, unsaturated bonds, and bridge-ring size are very sensitive to the cyclization rate. Additionally, aza- and norbornadienedicarboxylates demonstrate less reactivity, while thionorbornadienedicarboxylates show more reactivity with the challenge of their synthesis. The intermolecular version was also evaluated in comparison with the intramolecular version. Finally, our experimental tests verified the calculational prediction of the regioselectivity and reactivity.

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“…In another synthetically motivated study, Nicolaou, Houk and co-workers examined the Diels-Alder reactions of highly substituted dienes with juglone (5-hydroxy-1,4-naphthalenedione) dienophiles (Scheme 5). 7 Such a cycloaddition served as a key step in a recent total synthesis of bisanthraquinone antibiotic BE-43472B by Nicolaou. The regioselectivity of this reaction was of interest, since prior studies showed that typically, when juglones are dienophiles, the more nucleophilic diene terminus will attack C2 of the juglone (Scheme 5).…”

Section: Cycloaddition Reactions [2+2] Reactionsmentioning

confidence: 99%

Reaction mechanisms: pericyclic reactions

Tantillo

Lee

2011

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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This report surveys the 2010 literature on mechanisms of pericyclic reactions. Among the newer concepts highlighted in this year's studies are the distortion-interaction model of reactivity, the importance of CH-p interactions in controlling selectivity, and the catalysis of pericyclic reactions by transition metals and organocatalysts. This year, a substantial number of (4+3) cycloadditions and dyotropic rearrangements were examined; these reactions have received limited attention in the past.

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Origins of Regioselectivity of Diels−Alder Reactions for the Synthesis of Bisanthraquinone Antibiotic BE-43472B

Cited by 17 publications

References 25 publications

Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions

Enantioselective Redox‐Divergent Chiral Phosphoric Acid Catalyzed Quinone Diels–Alder Reactions

DFT and Experimental Exploration of Intramolecular [2 + 2 + 2] Cycloaddition of Oxanorbornadienedicarboxylates and Analogues

Reaction mechanisms: pericyclic reactions

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