Transition Metal‐Catalyzed Synthesis of 3‐Coumaranone‐Containing NH‐Aziridines from 2<i>H</i>‐Azirines: Nickel(II) versus Gold(I)

Sakharov, P. A.; Ростовский, Николай В.; Khlebnikov, Alexander F.; Khoroshilova, Olesya V.; Новиков, Михаил С.

doi:10.1002/adsc.201900366

Cited by 17 publications

(9 citation statements)

References 73 publications

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“…Other nitrogen-containing three-membered rings were employed by Novikov’s group in 2019, where they developed a method to construct 3-coumaranone containing NH-aziridines 614 in low to high yields from 2 H -azirines 613 and benzofurans 612 (Scheme a). Interestingly, the reaction also worked under Ni(II)-catalyzed conditions, however, Ph 3 PAuNTf 2 was the catalyst of choice for sterically hindered azirines (R 3 , R 4 = Me) and benzofurans containing electron-withdrawing groups (R 1 = 5-NO 2 and R 2 = CN).…”

Section: Gold-catalyzed Reactions Of Strained N-containing Heterocyclesmentioning

confidence: 99%

Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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The past decade has witnessed the golden age of homogeneous gold-catalyzed reactions, especially those that involve the transformation of highly strained molecules into complex molecular architectures. Gold catalysts, with unique electronic properties and catalytic abilities, have elevated versatile reaction modes through π-interaction induced activation. On the basis of increasing research interest in this topic, together with the significant development of various ligands, including phosphine ligands and azacyclic or noncyclic carbene ligands, the understanding of the catalytic function of gold catalysts has become much deeper and more comprehensive. Different reaction needs thus could be adapted by a novel gold catalyst with a diversified ligand selection. Furthermore, the whole evolution of the gold catalysis on synthetic methodologies has realized and expanded its application into natural product synthesis as well as the potentiality of drug discovery, which endows this ancient metal with a magnificent renaissance. The reactivity of strained small ring molecules with high tension has always been an important research topic in organic chemistry. When the highly strained small ring is linked with a π-electron rich moiety or contains a heteroatom, the gold activation of the π-system or coordination with the heteroatom can initiate a cascade reaction, usually followed by ring opening or expansion. These processes can result in the rapid construction of complex and distinct molecular structures, many of which feature in biologically important molecules. In this review, we will mainly summarize the advances on diverse reaction types and molecular constructions accomplished by homogeneous gold catalysis using highly strained substrates, including methylenecyclopropanes (MCPs), vinylidenecyclopropanes (VDCPs), cyclopropenes as well as aziridine- and epoxide-containing molecules, focusing on the last 10 years. For functionalized alkynyl cyclopropanes, several early inspiring and elegant examples will be described in this review for systematically understanding these transformations.

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Section: Gold-catalyzed Reactions Of Strained N-containing Heterocyclesmentioning

confidence: 99%

Gold-Catalyzed Conversion of Highly Strained Compounds

et al. 2020

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“… 616 Aziridines 478 have been also assembled by addition of 3-hydroxybenzofurans 476 to 2 H -azirines 477 catalyzed by gold(I) complexes ( Scheme 107 ). 617 …”

Section: Construction Of 3-membered Rings Catalyzed By Goldmentioning

confidence: 99%

“…616 Aziridines 478 have been also assembled by addition of 3-hydroxybenzofurans 476 to 2H-azirines 477 catalyzed by gold(I) complexes (Scheme 107). 617 Heterogeneous gold catalysis has also been successfully employed in the assembly of aziridines. For example, gold nanoparticles were reported to transfer nitrogen from ammonia to styrene, giving 2-phenylaziridine.…”

Section: Assembly Of Heteroatom-containing 3-membered Ringsmentioning

confidence: 99%

Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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Three- and four-membered rings, widespread motifs in nature and medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult to assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool to construct these highly strained carbocycles. This review aims to provide a comprehensive summary of all the major advances and discoveries made in the gold-catalyzed synthesis of cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their corresponding heterocyclic or heterosubstituted analogs.

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“…We assume that the reason for this lies in the removal of steric hindrances from one side of the azirine that, in conjunction with the high Lewis acidity of PPh 3 Au + , leads to the occurrence of side addition reactions with the azirine. 21 Thus, blocking the C2 position of the azirinecarboxylic acids 1 is crucially important for the gold-catalyzed synthesis of oxazinones 3.…”

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confidence: 99%

“…The gold-catalyzed reaction of an azirine-2-carboxylic acid having no additional substituent at the azirine C2 (R 2 = H) afforded a complex mixture of products, from which oxazinone 3k was isolated in very low yield. We assume that the reason for this lies in the removal of steric hindrances from one side of the azirine that, in conjunction with the high Lewis acidity of PPh 3 Au + , leads to the occurrence of side addition reactions with the azirine . Thus, blocking the C2 position of the azirinecarboxylic acids 1 is crucially important for the gold-catalyzed synthesis of oxazinones 3 .…”

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confidence: 99%

Gold vs Light: Chemodivergent Reactivity of Diazoesters toward 2H-Azirine-2-carboxylic Acids

et al. 2023

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An orthogonal reactivity of diazo compounds toward azirine-2-carboxylic acids, switching with the reaction conditions, is demonstrated. A gold-catalyzed reaction is Nselective and produces 1,3-oxazin-6-ones, whereas a blue light activation leads to O−H insertion products, azirine-2-carboxylic esters. The observed chemodivergence is explained by the metalbound and metal-free carbenes exhibiting different electronic properties in these reactions. In addition, a high antibacterial potential of the 1,3-oxazin-6-ones synthesized is shown.

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Transition Metal‐Catalyzed Synthesis of 3‐Coumaranone‐Containing NH‐Aziridines from 2H‐Azirines: Nickel(II) versus Gold(I)

Cited by 17 publications

References 73 publications

Gold-Catalyzed Conversion of Highly Strained Compounds

Gold-Catalyzed Conversion of Highly Strained Compounds

Gold-Catalyzed Synthesis of Small Rings

Gold vs Light: Chemodivergent Reactivity of Diazoesters toward 2H-Azirine-2-carboxylic Acids

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