Application of Chlorosulfonyl Isocyanate (CSI) in the Synthesis of Fused Tetracyclic Ketone Ring Systems DOI

Jennifer M. VanNatta,

Haichan Niu,

Graham J. Carlson

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15636 - 15651

Published: Oct. 10, 2024

Chlorosulfonyl isocyanate (CSI) is a complex reagent capable of facilitating numerous synthetic transformations, including lactam/lactone formation, sulfonylation, Friedel–Crafts-type acylations, and cycloadditions. Annulation reactions to form nitrogen-, oxygen-, sulfur-bearing heterocycles have been observed with CSI; however, the application CSI toward generation fused cyclic ketone ring systems has not previously reported. A serendipitous discovery pertinence occurred during structure–activity relationship campaign around our established lead benzosuberene-based molecule that functions as potent inhibitor tubulin polymerization. The benzylic olefin within this represents promising moiety for further functionalization. was initially investigated effect transformation its corresponding β-lactam functionality, but instead resulted in an unexpected tetracyclic system high yield (88%). This finding led exploration reactivity various arenes. Benzosuberene analogues varying functionalizations were synthesized treated CSI, all examples resulting except those bearing electron-withdrawing groups. Notably, simplified arene structures fewer substituents also undergo cyclization under these conditions. strategy approach synthesis appropriately functionalized systems.

Language: Английский

Lewis Acid‐Catalyzed Tandem Annulation of Propargylic Alcohols with 2‐Allylphenols and Their Anti‐tumor Activities DOI
Xiang Li,

Ning-Yu Guo,

Qing-Hui Liu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 19, 2024

Abstract A novel bismuth(III) trifluoro‐methanesulfonate‐catalyzed and environmentally benign synthetic strategy for the construction of a wide range structurally diverse, sophisticated [5,6,5]‐oxygen‐containing tricyclic frameworks with easy‐to handle propargylic alcohols 2‐allylphenols as substrates in presence Bi(OTf) 3 AgOTf is described. This Lewis acid catalyzed [3+2] annulation protocol, which tolerates great deal functional groups, proceeds through sequential Meyer‐Schuster rearrangement, nucleophilic substitution, 5‐ exo ‐trig cyclization, endo proton exchange sequences, affording versatile approach accessing oxygen‐containing skeletons moderate‐to‐excellent yields. In addition, most obtained compounds exhibited anti‐tumor activities against three types human cancer cell lines vitro , including Caco‐2 colon cells, MCF‐7 breast Hepg‐2 liver cells.

Language: Английский

Citations

0
Application of Chlorosulfonyl Isocyanate (CSI) in the Synthesis of Fused Tetracyclic Ketone Ring Systems DOI

Jennifer M. VanNatta,

Haichan Niu,

Graham J. Carlson

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15636 - 15651

Published: Oct. 10, 2024

Chlorosulfonyl isocyanate (CSI) is a complex reagent capable of facilitating numerous synthetic transformations, including lactam/lactone formation, sulfonylation, Friedel–Crafts-type acylations, and cycloadditions. Annulation reactions to form nitrogen-, oxygen-, sulfur-bearing heterocycles have been observed with CSI; however, the application CSI toward generation fused cyclic ketone ring systems has not previously reported. A serendipitous discovery pertinence occurred during structure–activity relationship campaign around our established lead benzosuberene-based molecule that functions as potent inhibitor tubulin polymerization. The benzylic olefin within this represents promising moiety for further functionalization. was initially investigated effect transformation its corresponding β-lactam functionality, but instead resulted in an unexpected tetracyclic system high yield (88%). This finding led exploration reactivity various arenes. Benzosuberene analogues varying functionalizations were synthesized treated CSI, all examples resulting except those bearing electron-withdrawing groups. Notably, simplified arene structures fewer substituents also undergo cyclization under these conditions. strategy approach synthesis appropriately functionalized systems.

Language: Английский

Citations

0