ChemInform Abstract: The Role of Cyclobutenes in Gold(I)‐Catalyzed Skeletal Rearrangement of 1,6‐Enynes.

Escribano-Cuesta, Ana; Pérez‐Galán, Patricia; Herrero‐Gómez, Elena; Sekine, Masaki; Braga, Ataualpa Albert Carmo; Maseras, Feliu; Echavarren, Antonio M.

doi:10.1002/chin.201302035

Cited by 1 publication

(4 citation statements)

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“…Mechanistically, the reaction begins with a regioselective O-attack to the β-carbon of the coordinated alkyne, forming cyclopropyl gold(I) carbene 721 (Scheme 157). As proposed for [2 + 2] cycloadditions, 699,700,716 this intermediate evolves by means of ring expansion leading to cyclobutene products 719. The same scenario was suggested for cyclopropylalkynes embedded into diyne scaffolds.…”

Section: Synthesis Of Cyclobutanesmentioning

confidence: 94%

“…211 Remarkably, bicyclo[3.2.0]hept-5-enes of type 654ac was formed from an alkyl-1,6-enyne bearing a trisubstituted alkene. 699 However, these were isolated examples, and in most of the cases, the gold(I)-catalyzed [2 + 2] cycloaddition of 1,6-enynes competes with other skeletal rearrangements, which prevent the selective formation of cyclobutenes (Scheme 142B). 643,699,700 The ligand employed was found to affect the regioselectivity of these transformations.…”

Section: Synthesis Of Cyclobutanesmentioning

confidence: 99%

“…699 However, these were isolated examples, and in most of the cases, the gold(I)-catalyzed [2 + 2] cycloaddition of 1,6-enynes competes with other skeletal rearrangements, which prevent the selective formation of cyclobutenes (Scheme 142B). 643,699,700 The ligand employed was found to affect the regioselectivity of these transformations. 699 Regarding the mechanism for the formation of cyclobutenes, computational studies revealed that the most favorable pathway begins with a 6-endo-dig cyclization to form cyclopropyl gold(I) carbene 657 (Scheme 143A).…”

Section: Synthesis Of Cyclobutanesmentioning

confidence: 99%

“…643,699,700 The ligand employed was found to affect the regioselectivity of these transformations. 699 Regarding the mechanism for the formation of cyclobutenes, computational studies revealed that the most favorable pathway begins with a 6-endo-dig cyclization to form cyclopropyl gold(I) carbene 657 (Scheme 143A). 699 This species evolves via ring expansion toward η 2 -(cyclobutene)gold(I) intermediate 658.…”

Section: Synthesis Of Cyclobutanesmentioning

confidence: 99%

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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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Section: Synthesis Of Cyclobutanesmentioning

confidence: 94%