Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

Leng, Bo; Chichetti, Stephanie M.; Su, Shun; Beeler, Aaron B.; Porco, John A.

doi:10.3762/bjoc.8.153

Cited by 5 publications

(3 citation statements)

References 26 publications

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“…2-Iodobenzaldehyde ( 4a ) was commercially available. 2-Iodo-4,5-dimethoxybenzaldehyde ( 4b ), 2-iodo-3,4,5-trimethoxybenzaldehyde ( 4c ), 2-[3-(but-2-ynyloxy)prop-1-ynyl]benzaldehyde ( 5l ), and N -(but-2-yn-1-yl)- N -[3-(2-formylphenyl)prop-2-yn-1-yl]-4-methylbenzenesulfonamide ( 5n ) were prepared by the literature methods.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of Colchicinoids and Allocolchicinoids through Rh(I)-Catalyzed [2+2+2+1] and [2+2+2] Cycloadditions of o-Phenylenetriynes with and without CO

et al. 2018

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The nonbenzenoid aromatics, tropones and tropolones, are found in various natural products such as colchicine and hinokitol, which possess significant biological activities. The traditional methods to construct the tropone skeletons include oxidation of cycloheptatriene and [4+3] cycloadditions. In addition, the total synthesis of colchicine and its analogues requires laborious organic transformations in the formations of 6-7-7 fused-ring systems. Transition metal-catalyzed carbocyclization and cycloaddition reactions have proven to be among the most efficient methods for constructing complex polycyclic systems. On the basis of our recent discovery of the Rh-catalyzed carbonylative [2+2+2+1] cycloaddition of triynes to the formation of a fused tropone system, we report here the application of this methodology to the one-step formation of the 6-7-7-5 fused tetracyclic scaffold of colchicinoids based on the [2+2+2+1] cycloaddition of o-phenylenetriynes with CO. In addition, the one-step formation of allocolchicinoids bearing the 6-7-6-5 fused tetracyclic system through the Rh-catalyzed [2+2+2] cycloaddition of o-phenylenetriynes is also described.

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Section: Methodsmentioning

confidence: 99%

“…2-Iodobenzaldehyde (4a) was commercially available. 2-Iodo-4,5-dimethoxybenzaldehyde (4b), 43 2-iodo-3,4,5trimethoxybenzaldehyde (4c), 29 2-[3-(but-2-ynyloxy)prop-1-ynyl]benzaldehyde (5l), 44 and 44 were prepared by the literature methods.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis of Colchicinoids and Allocolchicinoids through Rh(I)-Catalyzed [2+2+2+1] and [2+2+2] Cycloadditions of o-Phenylenetriynes with and without CO

et al. 2018

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“…In our early approach, we followed one of the most studied pathways that implies the transition metal-catalyzed cyclization of ortho -carbonylalkynylaryls in the presence of selected nucleophiles (Scheme ). − However, while most of contributions in this field include C, N, and O nucleophiles, , ours employs a hydride transfer from Hantzsch ester (HEH). , …”

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Access to 1H-Isochromenes: Reaction Development and Mechanistic Insight

et al. 2016

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The gold-catalyzed domino cyclization/nucleophilic reaction of ortho-carbonylalkynylaryls has been studied. Thus, 2-(pyridin-2-ylethynyl)benzaldehyde has been chosen to isolate key intermediates that may take part in the reaction mechanism. Employing Hantzsch ester (HEH) as nucleophile, it has been impossible to isolate the corresponding gold–alkenyl specie; however, when methanol was used as solvent (and nucleophile), the expected chelate gold–vinyl complex was isolated and unambiguously characterized by X-ray analysis. When HEH is present in the alcoholic reaction mixture, isotopic studies show that the cleavage of the Au–C bond of gold–vinyl complex proceeds through a protodemetalation pathway, rather than a plausible metal–hydride reductive elimination mechanism. Finally, with the aim of broadening the scope of the cyclization/reduction reaction previously reported, we present that the catalytic system is robust and applicable for a diverse family of challenging substrates presenting ester, aldehyde, ether, alkene, and alkyne functionalities.

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Gold‐Catalyzed Cyclizations of Alkynes with Alkenes and Arenes

et al. 2017

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Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

Cited by 5 publications

References 26 publications

Synthesis of Colchicinoids and Allocolchicinoids through Rh(I)-Catalyzed [2+2+2+1] and [2+2+2] Cycloadditions of o-Phenylenetriynes with and without CO

Synthesis of Colchicinoids and Allocolchicinoids through Rh(I)-Catalyzed [2+2+2+1] and [2+2+2] Cycloadditions of o-Phenylenetriynes with and without CO

Gold-Catalyzed Access to 1H-Isochromenes: Reaction Development and Mechanistic Insight

Gold‐Catalyzed Cyclizations of Alkynes with Alkenes and Arenes

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