Cyclobutanols rearrangement

The trimethylsilyl ethers 212 of four-membered 1-alkenyl-1-cyclobutanols rearrange to the ring-expanded 0-mercuriocyclopentanones 213. These can be converted into the a-methylenecyclopentanones 214 through elimination or further expanded by one-carbon atom into cyclohexanones 215 via the Bu3SnH-mediated free radical chain reactions [116]. A similar radical intermediate is suggested to be involved in the ring expansion of a-bromomethyl-fi-keto esters [117]. (Scheme 84)... 

Conversion of pregnanes to androstanes via the Schmidt Rearrangement 17/3-aminoandrost-5-en-3/3-ol, 145 Cyclobutanol formation by ketone irradiations... 

A lower molecular weight methyl ketone and an olefin are isolated as products of this reaction. That the enol is formed as a primary product which rearranges to the ketone follows from its detection in the IR spectrum of gaseous 2-pentanone upon photolysis. 3 In addition to the ketone and olefinic products, one usually obtains varying amounts of cyclobutanols. 

The alkoxide generated by KH in THF was believed to be effective in accelerating the vinylcyclobutane ring expansion in the synthesis of 6-membered ring compounds 142). As an example, the cyclobutanol (416) reacted with KH and rearranged to (417), which upon subsequent oxidation, provided (418) 142) in 64.5% yield. The a,P-unsaturated ketone (418) was converted to (—)- 3-selinene (419)142). Similarly, furancyclohexanol (421) could be obtained from the cyclobutanol (420) 142). 

Dihydro-2,3-methano-l,4-naphthoquinones 15 rearrange to cyclobutanols 16 on irradiation. The reaction is. at least in part, reversible, as the excited cyclobutanol undergoes ring opening and disproportionation back to starting material.15 16... 

The preparation of cyclobutanols by a homoallyl rearrangement has been described previously (see Houben-Weyl. Vol. 4/4, p 62), e.g. treatment of the but-3-enyl p-toluenesulfonate 1 with potassium methoxide in dioxane yielded the dicyanomethoxycyclobutane derivative 2 (61 %). It is also possible to introduce hydrogen into the cyclobutane product by the use of hydrides, for example, borohydrides. Methoxy- or ethoxy-substituted cyclobutanes are formed with alkoxides, while cyano compounds are obtained with potassium cyanide (Table 1). Electronegative substituents in the 1-position of the starting alkene are necessary for a good result in this preparative method. 

Byproducts of this rearrangement are cyclobutenes, cyclopropane derivatives and allenic alcohols. The ratio of these products depends on the substitution of the substrate and on the reaction conditions. For example, 3-methyl-5-tosyloxypenta-l,2-diene (3) gives 75% of 1-methyl-2-methylenecyclobutanol (4) upon hydrolysis with water and calcium carbonate at 100 °C, while acetolysis with acetic acid/sodium acetate at 80 °C, and subsequent treatment with lithium aluminum hydride, provides only 37% of the cyclobutanol.12... 

Solvolysis of l-ethenylidene-3-tosyloxycycloalkanes 13 gives cyclobutanols of the bicy-clo[n.l.l]alkanol and bicyclo[n.2.0]alkanol series.14 In this reaction, the competing 1234-1243 rearrangement leads to the bicyclo[n.2.0]alkanols 15. The yield for the homoallyl rearrangement product 14, after hydrolysis, is 9% when n = 3 and 37% when n = 4. 

The same mode of migration is found if the rc-bond needed for rearrangement is part of an aryl ring in the 2-position. Usually only the substituted C3 of cyclobutanones (Table 5)71 74,140 or cyclobutanols (Table 6)75 migrates on treatment with trifluoroaeetic acid,73 methanesulfonic acid,71 trifluoromethanesulfonie acid, 140/ -toluenesulfonic acid,74 phosphorus pentoxide,71-74 and tin(IV) chloride,72 generally with diethyl ether or benzene as the solvent. 

Somewhat similar rearrangements involving a cyclobutanol ring have been proposed earlier P. Buchschacher, M. Cereghetti, H. Wehrli, K. Schaffner, and 0. Jeger, Helv. Chim. Acta, 42, 2122 (1959) P. DeMayo and S. T. Reid, Quart. Rev., 15, 393 (1961). 

The subsequent dark reactions readily are understood as typical of diradicals. Cleavage of 1 at Ca-CB gives ethene and an enol, which rearranges to the ketone. Alternatively, 1 can cyclize to a cyclobutanol ... 

Whatever the case, the formation of the cyclooctenone 320 from the cyclobutanone 317 constituted the first example of a one-step C4 — C8 ring expansion. In the same way, the spirocyclobutanone 266 63,73), was treated with vinylmagnesium bromide to generate a mixture of the diastereomeric cyclobutanols 322 and 323 in 78% yield (ratio 21/79). Each diastereomer, separated by HPLC, individually subjected to KH in THF at room temperature, rearranged cleanly to bicyclo[5.3. l]undec-l(l l)-en-4-one in 80% yield, Eq. (87)161>. 

No cyclobutanol derivative was formed. It was proposed that the degenerate cyclopropylcarbinyl rearrangement proceeded via the bicyclobutonium ion [127]. 

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