Intramolecular asymmetric oxidopyrylium-based [5 + 2] cycloadditions

Rokey, Samantha N.; Simanis, Justin A.; Law, Chunyin; Pohani, Shilpa; Behrends, Samantha Willens; Bulandr, Jacob J.; Ferrence, Gregory M.; Goodell, John R.; Mitchell, T. Andrew

doi:10.1016/j.tetlet.2020.152377

Cited by 4 publications

(2 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As part of our research program directed toward [5+2] cycloadditions [ 78 , 79 , 80 , 81 , 82 , 83 , 84 ] we explored mechanistic pathways of acetoxypyranone-derived oxidopyrylium species en route to [5+2] cycloadditions [ 81 ] that led to the discovery of polycyclic ether-benzopyran 4 ( Scheme 1 ). Commercially available aldehyde 2 was treated with 2-furyllithium to provide the desired alcohol (not shown) in quantitative yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Polycyclic Ether-Benzopyrans and In Vitro Inhibitory Activity against Leishmania tarentolae

et al. 2020

Self Cite

View full text Add to dashboard Cite

Construction of a focused library of polycyclic ether-benzopyrans was undertaken in order to discover new therapeutic compounds that affect Leishmania growth and infectivity. This is especially of interest since there are few drug therapies for leishmaniasis that do not have serious drawbacks such high cost, side effects, and emerging drug resistance. The construction of these polycyclic ether-benzopyrans utilized an acetoxypyranone-alkene [5+2] cycloaddition and the Suzuki-Miyaura cross-coupling. The multi-gram quantity of the requisite aryl bromide was obtained followed by effective Pd-catalyzed coupling with boronic acid derivatives. Compounds were tested in vitro using the parasitic protozoan, Leishmania tarentolae. Effects of concentration, time, and exposure to light were evaluated. In addition, the effects on secreted acid phosphatase activity and nitric oxide production were investigated, since both have been implicated in parasite infectivity. The data presented herein are indicative of disruption of the Leishmania tarentolae and thus provide impetus for the development and testing of a more extensive library.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of Polycyclic Ether-Benzopyrans and In Vitro Inhibitory Activity against Leishmania tarentolae

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…In 2020, Rokey with colleagues presented intramolecular asymmetric oxidopyrylium-based [5 + 2] cycloadditions. [32] Chiral enamines 108, derived from corresponding silyloxypyrones with aldehyde group 107, allow product 109 to perform the most selective reactions. The formation of tetrahydrofuran fragment occurred under mild conditions (Scheme 33).…”

Section: Synthesis Of O-heterocyclesmentioning

confidence: 99%

Cycloaddition Reactions of Enamines

et al. 2023

View full text Add to dashboard Cite

This review includes information for around two last decades on cycloaddition reactions of enamines with various agents in order to build carbo‐ and heterocycles. In addition, the review presents organo‐catalytic reactions in which enamines are intermediate products generated in situ. This review covers the synthesis of four, five, six and eight‐membered carbocyclic compounds, as well as heterocycles as pyrroles, pyridines, etc.

show abstract

Experimental and Theoretical Investigation of the Synchronicity of Ambident Silyloxypyrone-Based (5 + 2) Cycloadditions

et al. 2023

Self Cite

View full text Add to dashboard Cite

The reaction pathway of silyloxypyrone-based (5 + 2) cycloadditions was determined to be extremely dependent on the nature of the dipolarophile. Neutral alkenes were the least reactive, whereas both electron-deficient and electron-rich dipolarophiles were more reactive, thus providing evidence for ambident oxidopyrylium intermediates. Qualitative rate studies, Hammett linear free energy relationships, and theoretical calculations combined to provide evidence for a spectrum of reactivity that passes through the borderlands of concerted and stepwise.

show abstract

Intramolecular asymmetric oxidopyrylium-based [5 + 2] cycloadditions

Cited by 4 publications

References 47 publications

Synthesis of Polycyclic Ether-Benzopyrans and In Vitro Inhibitory Activity against Leishmania tarentolae

Synthesis of Polycyclic Ether-Benzopyrans and In Vitro Inhibitory Activity against Leishmania tarentolae

Cycloaddition Reactions of Enamines

Experimental and Theoretical Investigation of the Synchronicity of Ambident Silyloxypyrone-Based (5 + 2) Cycloadditions

Contact Info

Product

Resources

About