The (4 + 2) cycloaddition of ketenes and .beta.-methoxy .alpha.,.beta.-unsaturated ketones: 2-pyranones

Brady, William T.; Agho, Michael O.

doi:10.1021/jo00174a034

Cited by 21 publications

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“…Transition-metal-catalyzed allene–diene cycloaddition reactions, although recent in their discovery, have circumvented this competition and become a mainstay of new process developments . Ketenes readily undergo [2 + 2]-cycloaddition and, recently, [4 + 2]-cycloaddition reactions, but for the latter only with highly activated diene equivalents or with the aid of suitable catalysts . In contrast, diazo compounds commonly react with one double bond of dienes by dipolar cycloaddition or, following dinitrogen extrusion, by cyclopropanation (Scheme ), but not by [4 + 2]-cycloaddition.…”

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confidence: 99%

Unprecedented Intramolecular [4 + 2]-Cycloaddition between a 1,3-Diene and a Diazo Ester

et al. 2016

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Diazo compounds that are well-known to undergo [3 + 2]-cycloaddition provide the first examples of the previously unknown [4 + 2]-cycloaddition with dienes that occur thermally under mild conditions and in high yields. Reactions are initiated from reactants prepared from propargyl aryldiazoacetates that undergo gold(I)-catalyzed rearrangement to activated 1,3-dienyl aryldiazoacetates. These reactions proceed to mixtures of both [4 + 2]-cycloaddition and the 1,3-dienyl aryldiazoacetate after long reaction times. At short reaction times, however, both E- and Z-1,3-dienyl aryldiazoacetates are formed and, after isolation, thermal reactions with the E-isomers form the products from [4 + 2]-cycloaddition with ΔH(‡)298 = 15.6 kcal/mol and ΔS(‡)298 = -27.3 cal/(mol·°C). The Z-isomer is inert to [4 + 2]-cycloaddition under these conditions. The Hammett relationships from aryl-substituted diazo esters (ρ = +0.89) and aryl-substituted dienes (ρ = -1.65) are consistent with the dipolar nature of this transformation.

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confidence: 99%

Unprecedented Intramolecular [4 + 2]-Cycloaddition between a 1,3-Diene and a Diazo Ester

et al. 2016

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“…Compound 19f was prepared by the method described for 19a using CF 2 Br 2 (5.05 g, 24.1 mmol), microwave-dried molecular sieves (4 Å ) powder (2.41 g), THF (20 mL), P(NMe 2 ) 3 (7.87 g, 28.2 mmol), and 2-methyl-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carbaldehyde (18f, 2.30 g, 12.1 mmol), prepared according to a reported procedure [33] from 2-hydroxymethylene-3,4-dihydro-2H-naphthalen-1-one [34]. The mixture was stirred at room temperature for 1.…”

Section: -(22-difluorovinyl)-2-methyl-34-dihydronaphthalen-1(2h)-omentioning

confidence: 99%

Heck-type 5-endo-trig cyclizations promoted by vinylic fluorines: Ring-fluorinated indene and 3H-pyrrole syntheses from 1,1-difluoro-1-alkenes

Ichikawa

Sakoda

Mihara

et al. 2006

Journal of Fluorine Chemistry

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Ketene Cycloadditions

1994

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The reaction of ketene with itself was described almost simultaneously in 1908 by Chick and Wilsmore in England, and by Staudinger and Klever in Germany; priority for the discovery was attributed to Wilsmore by the German group. Ketene cycloaddition was an early example of a peculiar process, one that formed carbon–carbon bonds with ease, often without the need for solvent, catalyst, or high heat. Subsequent work by others was done in the shadow of Staudinger's exhaustive and rigorous study of all phases of ketene reactivity. Three factors led to a resurgence of interest in this reaction beginning in the 1960s. Haloketenes, which had previously eluded study, were found to have high reactivity, and the halogens could easily be removed after the reaction. The increasing sophistication of powerful analytical methods, particularly nuclear magnetic resonance spectroscopy, led to discovery of the interesting stereochemical aspects of this reaction. Finally, the new theory of orbital symmetry conservation provided a conceptual framework to rationalize these puzzling “no mechanism” reactions. This chapter is a review of cycloaddition reactions of ketenes. Here, a cycloaddition is defined as a reaction of a ketene with an unsaturated organic compound to give a cyclic product by a mechanism that, in principle, involves the almost simultaneous formation of two bonds between two reactants. While there is no concern here as to whether bond formation is concerted or stepwise, no other chemical process can take place between the formation of the first and second bond. Definition here involves both structural and mechanistic factors, and it is difficult to avoid a certain amount of arbitrariness. Products, such as dehydroacetic acid, which seem to us to arise by concatenation of ketene molecules followed by cyclization are excluded. These reactions, are more properly considered to arise from a series of ionic reactions, and the prediction of the eventual product does not take advantage of the special mechanistic features commonly associated with true cycloadditions. Additions to imines to give β‐lactams are numerous and will be covered in a separate review. The literature has been searched to the end of 1988. Many reviews devoted partially or exclusively to ketene cycloadditions have been published. Specific topics that have been reviewed include haloketenes, fluoroketenes, cyanoketenes, intramolecular cycloadditions, conjugated ketenes, and β‐lactam antibiotics. Ancillary topics pertinent to ketene cycloadditions that have been reviewed include cycloreversion reactions, ketene equivalents, which provide ketene functionality with olefin‐like reactivity especially in [4 + 2] reactions, application of frontier molecular orbital theory to cycloadditions, and a critical discussion of cycloadditions with polar intermediates. Applications of cyclobutanones in synthesis have also been reviewed.

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The (4 + 2) cycloaddition of ketenes and .beta.-methoxy .alpha.,.beta.-unsaturated ketones: 2-pyranones

Cited by 21 publications

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Unprecedented Intramolecular [4 + 2]-Cycloaddition between a 1,3-Diene and a Diazo Ester

Unprecedented Intramolecular [4 + 2]-Cycloaddition between a 1,3-Diene and a Diazo Ester

Heck-type 5-endo-trig cyclizations promoted by vinylic fluorines: Ring-fluorinated indene and 3H-pyrrole syntheses from 1,1-difluoro-1-alkenes

Ketene Cycloadditions

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