Cyclopropylcarbinyl cyclobutyl rearrangements

However, a detailed discussion of the cyclobutyl-cyclopropylcarbinyl rearrangement is beyond the scope of this chapter and the following discussion will therefore be confined to the formation of cyclobutane derivatives only. 

In accordance with the previous observations of Dauben and Schleyer the cyclopropylcarbinyl-cyclobutyl cation rearrangement proceeds with net inversion at the migration origin upon nucleophilic attack. 

Vincovic and Majerski prepared a second [3.1.1]propellane 165 from pyrolysis of 166 This system is more strained than the parent 158, decomposing in 30 minutes at room temperature in benzene. It reacts with HCl at — 80°C to yield only the nortricyclylmethyl chloride 167. Although this appears to involve external opening, rather than cleavage of the central propellane bond, protonation of the central bond to give 168 followed by cyclobutyl to cyclopropylcarbinyl rearrangement can also provide 167. 

An ion cyclotron resonance study of ion-molecule reactions in benzene has shown that the cyclopropenyl cation arises from a a-type complex between protonated benzene and benzene. The mass spectral fragmentation of cyclopropanol monoethers has been examined and subjected to theoretical study and the fragmentation of a series of underivatized aminocyclitol-aminoglycoside antibiotics is believed to involve the ion (387). The chemical ionization mass spectrum of oct-6-en-3-one has been interpreted as involving the cyclobutyl-cyclopropylcarbinyl cation rearrangement (388)- (389). ... 

It is relevant to discuss briefly at this point the stereochemistry and mechanism of the cyclopropylcarbinyl-cyclobutyl-homoallyl rearrangements. Solvolysis of cyclopropylcarbinyl, cyclobutyl, and homoallyl derivatives bearing stereospecific labels or substituents lead to rearranged products in which the stereochemical relationships in the starting material are retained (74—76). The stereochemistry is illustrated below with the hydrolysis of specifically deuterated cyclopropylcarbinyl methanesulfonate... 

The rearrangement of the intermediate alkyl cation by hydrogen or methyl shift and the cyclization to a cyclopropane by a CH-insertion has been studied by deuterium labelling [298]. The electrolysis of cyclopropylacetic acid, allylacetic acid or cyclo-butanecarboxylic acid leads to mixtures of cyclopropylcarbinyl-, cyclobutyl- and butenylacetamides [299]. The results are interpreted in terms of a rapid isomerization of the carbocation as long as it is adsorbed at the electrode, whilst isomerization is inhibited by desorption, which is followed by fast solvolysis. 

Cyclopropylcarbinyl chloride rearranges to cyclobutyl and allylcarbinyl chlorides over NaY zeolite at room temperature. This result is consistent with ionization of the... 

Artemisyl, Santolinyl, Lavandulyl, and Chrysanthemyl Derivatives.— The presence of (41) in lavender oil has been reported earlier. Poulter has published the full details of his work (Vol. 5, p. 14) on synthetic and stereochemical aspects of chrysanthemyl ester and alkoxypyridinium salt solvolyses (Vol. 3, pp. 20—22) and discussed its biosynthetic implications. Over 98% of the solvolysis products are now reported to be artemisyl derivatives which are formed from the primary cyclopropylcarbinyl ion (93) which results from predominant (86%) ionization of the antiperiplanar conformation of (21)-)V-methyl-4-pyridinium iodide the tail-to-tail product (96 0.01%) may then result from the suprafacial migration of the cyclopropane ring bond as shown stereochemically in Scheme 3. This is consistent with earlier work (Vol. 7, p. 20, ref, 214) reporting the efficient rearrangement of the cyclobutyl cation (94) to (96) and its allylic isomer, via the tertiary cyclopropylcarbinyl cation (95). ... 

From solvolytic studies of iso topically labeled substrates it was shown that cyclopropyl-carbinyl-cyclobutyl interconversion is stereospecific51 52. The stereospecific interconversion of cyclobutyl cations to the corresponding cyclopropylcarbinyl cation was also cleanly observed in superacid medium, and was used to prepare otherwise unstable cis-(a-methylcyclopropyl)carbinyl cation 1753. Thus ionization of d.s-2-chloro- or cw-3-chloro-l-methylcyclobutane in SbF5-S02ClF at -135 °C yielded the ris-isomer which rapidly rearranged irreversibly into the trans-isomer 18 at about -100 °C. The trows-isomer 18 is the only cation obtained when the preparation was carried out at -80 °C, or when prepared from the cyclopropylmethyl carbinol20b 38 50ac (equation 24). 

The secondary ion 82 shows degenerate equilibration at -45 °C (8-line l3C NMR spectrum), but is static at -110 °C. It was shown that the rearrangement takes place through the participation of the C3—C4 bond rather than the C2—C3 bond, and thus through a cyclopropylcarbinyl-cyclobutyl interconversion57 (equation 49). 

A set of rapidly equilibrating carbenium ions might account for the rearrangements and the label scrambling but this cannot be the correct explanation, for cyclopropylcarbinyl, cyclobutyl, and allylcarbinyl systems all solvolyze much more rapidly than would be expected from model compounds. Thus, for example, the rate of solvolysis of cyclopropylcarbinyl tosylate is 10 times that of the solvent-assisted solvolysis of isobutyl tosylate.77 Cyclobutyl tosylate solvolyzes 11 times... 

The parent 3-homonortricyclyl cation [147] underwent three-fold degenerate rearrangements in superacids, as shown by its temperature dependent nmr spectra, but only at higher temperatures (—85°C to 20 C) than for the corresponding dehydrohomoadamantyl [144 R = H] and dehydroadamantyl cations [126 X = H], The lower rearrangement rate of [147] was explained by a less favourable formation of the puckered cyclobutyl cation intermediates [159] in this geometrically more constrained system. The assignment of a symmetrical cyclopropylcarbinyl cationic structure to [147] was confirmed by comparison of its and C-nmr spectra with the static counterparts [157]. 

The investigations carried out in this area were done primarily to determine the magnitudes of steric and electronic effects on the solvolytic rates and products of reaction in the cyclopropylcarbinyl cation system. The goal of most of these studies was to learn more about the nature of the charge delocalization in the cyclopropylcarbinyl system and of the stereochemistry of the cyclopropylcarbinyl-cyclobutyl and cyclopropyl-carbinyl-allylcarbinyl cation rearrangements. Key papers in these studies were those in 1966 by Schleyer and Van Dine, in 1971 by Majerski and Schleyer and in 1974 by Poulter and Spillner which demonstrated that in the simple cyclopropylcarbinyl system... 

Paquette and coworkers have carried out a solvolytic study of a tricyclic system in which a 3,4-ethano group is attached to the 2-bicyclo[3.1.0]hexyl system. This was done to assess the importance of cyclopropyl versus cyclobutyl neighboring group involvement. Some relative rate data are given in Scheme 10 for 3,5-dinitrobenzoate hydrolyses in 80 % aqueous acetone at 115 °C. Product results are also shown. Deuterium labeling revealed the lack of any cyclopropylcarbinyl-cyclopropylcarbinyl cation rearrangements. Also, the results showed that cyclopropyl participation predominates over initial involvement of the cyclobutyl group. 

The solvolysis of both cyclopropylcarbinyl and cyclobutyl derivatives proceeds with rearrangement to give mixtures of cyclopropylcarbinyl (515), cyclobutyl (516), and allylcarbinyl derivatives (517)401,402. Under certain conditions the product distributions are very similar, starting from either (57. ) or (514) (Table 16). These data... 

A wide variety of hydroxylamines, e.g. 7V-phenylhydroxylamine, 0-benzoyl-A-ter/-butylhy-droxylamine, and A-(a-cyanoalkyl)hydroxylamines, added smoothly to cyclopropanone or 1-acetoxycyclopropanol to form the adducts 13, 15 and 17, which were conveniently converted into -lactams 14, 16 and 19 a procedure which resembles the cyclopropylcarbinyl cyclobutyl rearrangement. The former two reagents gave hydroxyamine-type adducts 13 and 15, which rearranged spontaneously into )5-lactams, while with the latter reagent subsequent reaction of the adduct 17 with p-toluenesulfonyl chloride was required to form a species 18 which easily underwent ring enlargement. ... 

Dugan et al. (1965) have proposed that marasmic acid (I) is formed in nature from the cyclobutyl cation II, also a suspected precursor of illudin S and M, which occur in closely related fungi. In the marasmic acid case, II rearranges to give the alternate cyclopropylcarbinyl system, as in III and I. Oxidations at the starred carbons in III give marasmic acid (I). 

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