Silver cationic rearrangements

Silver trifluoroacetate is a suitable catalyst for various cationic rearrangements involving multiple carbon-carbon bonds [49 5(1] In the presence of silver trifluoroacetate, 2 propynyl acetates rearrange to the butadienyl acetates to give dienes that are useful in Diels-Alder reactions [49] (equation 22)... 

This silver-catalyzed ring rearrangement could be explained by preferential interaction of the silver cation with the most substituted edge of the cyclopropane to form an argento cation. In the latter, the presence of C-Si or Ge bond with the right orientation stabilized the cation sufficiently so that it classically evolved through (3-H... 

As for the cyclopropane rearrangement, the reaction probably involved the formation of a cationic silver cationic species followed by regioselective o-bond migration, leading preferentially to the more stable carbocation intermediate that is finally intramolecularly trapped by the organosilver species (Scheme 3.25).39... 

Similarly, numerous other oligocyclic ring systems containing cyclopropane units have been obtained according to this method.The reaction is mechanistically interpreted as occurring via edge attack of the silver ion followed by a cationic rearrangement. Softer metal catalysts, such as rhodium, nickel and palladium, mostly lead to alternative products (e.g. [2-F2] cycloreversion). ... 

The reactive cyclopropylidene cyclopropylcarbinyl cation 37 was generated from the corresponding bromide and silver hexafluoroantimonate, and was reacted in situ with olefins such as cyclohexene to form the addition products (equation 33). On the other hand, under the same conditions, the isopropylidene cyclopropylcarbinyl cation 41 rearranged spontaneously by ring expansion (equation 34)71. 

Strained cyclic systems such as cyclopropane derivatives proved sensitive to silver ions. Indeed, silver usually induced ring opening of cyclopropanes, leading to argento cationic intermediates, which evolved further depending on substituents. Most, if not all, of these ring rearrangements resulted from initial formation of a a complex of the cyclopropane with silver ion. 

In contrast to the preceding mechanisms proposed for [3,3]-sigmatropic shifts, the mechanism of the silver-catalyzed oxy-Cope rearrangement was proposed as a stepwise process (Scheme 3.37). As usual, the reaction would be initiated by silver coordination to the alkyne moiety. Nucleophilic attack of this complex by the double bond would then lead to a cyclic cationic vinylsilver intermediate. Fragmentation would then give the dienone. 

This reaction exhibits strong analogy with the silver-promoted cationic aza-Cope rearrangement described by Overman et al. As a new route toward alkaloids, these authors showed thatcyanomethylamines carrying unsaturated chain led to pyrrolidine or piperidine derivatives on treatment with silver salts depending on the substituent (Scheme 3.38) 59 60... 

Therefore, from epoxide 83 (Scheme 5.38), a 1,2-phenyl shift in intermediate MM would provide oxonium derivative NN, which would furnish, after rearrangement of the oxetane intermediate OO, the desired ketone 84. It is interesting to note that on the same substrates cationic gold derivatives (activated with silver salts) did not lead to the same final compounds, showing the unique reactivity of silver salts. 

This rearrangement must occur by heterolytic cleavage of the carbon-chlorine bond in 19 to yield the intermediate cation 6+, which is then attacked by the nucleophilic chloride at one of the partially positively charged cyclopropyl groups. With the less nudeophilic tetrafluoroborate counterion, generated by treating 19 with silver tetrafluoroborate under sol-... 

A related reaction occurs on irradiation of a hypochlorite (Scheme 2). The alkoxyl radical can again abstract a hydrogen atom in a l,S-shift, and the final chloro alcohol can be cyclized to form a tetrahydro-furan. Some processes lead directly to the cyclic product For instance, an alcohol with an accessible 8-hydrogen can be directly converted to a tetrahydrofuran on refluxing with lead tetraacetate. In a related reaction, treatment of an alcohol with silver carbonate and bromine can lead to the cyclic ether by initial formation of a hypohalite. The cyclization occurs when the rearranged radical is converted to a cation, either by oxidation with Pb(OAc)4 or by silver-assisted loss of halide ion. Hypoiodites are also fiequent-ly used, generated in situ. ... 

A number of biomimetic syntheses have included Wagner-Meerwein rearrangements. A chemical conversion of humulene (48) to sterpurene (50) involved an interesting series of Wagner-Meerwein rearrangements (see Scheme 19).- - Humulene (48) was converted to the cyclooctenol (51) and thence to the bromide (52) via the protoilludyl cation (49). Treatment of (52) with silver acetate in acetic acid gave racemic sterpurene (50). In contrast the epimeric bromide (53) gave (54). 

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