An Acylal of Dimethylketene

Bestian, H.; Günther, Dieter

doi:10.1002/anie.196306081

Cited by 20 publications

(2 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The author gratefully acknowledges Professor Lionel Salem (Orsay) for his comments and criticisms on the manuscript. (12) H12C2 refers to the line bisecting the plane formed by carbon 2 and hydrogens 1 and 2. Acknowledgment.…”

mentioning

confidence: 99%

Solvolysis of trans-2,2-dimethyl-3-(2'-methylpropenyl)cyclobutyl tosylate. Model reactions relevant to squalene biosynthesis

Rm¹,

Wh²

1972

J. Am. Chem. Soc.

View full text Add to dashboard Cite

mentioning

confidence: 99%

Solvolysis of trans-2,2-dimethyl-3-(2'-methylpropenyl)cyclobutyl tosylate. Model reactions relevant to squalene biosynthesis

Rm¹,

Wh²

1972

J. Am. Chem. Soc.

View full text Add to dashboard Cite

“…We decided that it was advantageous to construct the cyclobutane ring early in the synthesis; the 2+2 cycloaddition with dimethylketene was tried first converting 2,2-dimethylmalonic acid thermally to dimethylketene acylal, followed by treatment of the latter with K 2 CO 3 in the presence of 1,5-hexadiene 6 at 120 °C. 8 Under these conditions only minute amounts of the desired cyclobutanone were formed. We next tried the cycloaddition by the dehydrochlorination of isobutyryl chloride with NEt 3 .…”

Section: Resultsmentioning

confidence: 99%

First ketene cycloaddition approach to (±)-junionone

Erden

Watson

2016

Tetrahedron Letters

View full text Add to dashboard Cite

Junionone is the first monocyclic cyclobutane monoterpenoid isolated from a plant. Of the existing four syntheses of this compound, none employs a ketene cycloaddition to construct the four-membered ring. Herein, we report the first total synthesis of junionone that features a ketene cycloaddition for the synthesis of this compound, starting from the commercially available 1,5-hexadiene. 2009 Elsevier Ltd. All rights reserved.

show abstract

Ketene Cycloadditions

1994

View full text Add to dashboard Cite

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.

show abstract

An Acylal of Dimethylketene

Cited by 20 publications

References 17 publications

Solvolysis of trans-2,2-dimethyl-3-(2'-methylpropenyl)cyclobutyl tosylate. Model reactions relevant to squalene biosynthesis

Solvolysis of trans-2,2-dimethyl-3-(2'-methylpropenyl)cyclobutyl tosylate. Model reactions relevant to squalene biosynthesis

First ketene cycloaddition approach to (±)-junionone

Ketene Cycloadditions

Contact Info

Product

Resources

About