Search results for "Site selectivity"
showing 3 items of 3 documents
Unveiling the Chemo‐ and Regioselectivity of the [3+2] Cycloaddition Reaction between 4‐Chlorobenzonitrile Oxide and β‐Aminocinnamonitrile with a MED…
2021
Site-selectivity control in hetero-Diels-Alder reactions of methylidene derivatives of lawsone through modification of the reactive carbonyl group: a…
2019
A new perspective on the reactivity of hydroxyquinones was revealed as an acetal derivative of lawsone was synthesized, isolated, and used in tandem Knoevenagel/hetero-Diels-Alder reactions catalyzed by S-proline. The intermediate alkylidene-1,3-diones that were formed in situ reacted with electron rich alkenes to predominantly afford pyrano-1,2-naphthoquinone (β-lapachone) derivatives along with the isomeric pyrano-1,4-naphthoquinone (α-lapachone) derivatives in high to excellent total yields. Interestingly, the highly reactive arylidene-1,3-dione derivatives were found to be stable and isolable. DFT calculations suggest that these hetero-Diels-Alder reactions have a high polar character, …
1,3-Dipolar cycloadditions with meso-tetraarylchlorins – site selectivity and mixed bisadducts
2017
The 1,3-dipolar cycloaddition reaction of meso-tetraarylporphyrins with nitrones gives isoxazolidine-fused chlorins. Depending on the substitution pattern on the meso-aryl groups and the nitrone, the chlorins can be obtained in high yields (up to 91%). Bacteriochlorin-type bisadducts are also obtained, although in low yield, from the reaction of meso-tetrakis(pentafluorophenyl)porphyrin with N-methyl, N-cyclohexyl or N-benzyl nitrone. The structure of a bis(N-benzyl isoxazolidine-fused) bacteriochlorin was determined by single-crystal X-ray diffraction and rationalized by DFT calculations. To further explore the nature of site selectivity in the formation of bisadducts, isomeric mixed bacte…