Patai S., Rappoport Z. 2000 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 2 / 0257 328

V.DI-p-METHANE PROCESSES

A.Open-chain Systems

Perhaps one of the most ubiquitous photochemical reactions undergone by nonconjugated dienes is that encountered in the 1,4-diene system. This is referred to as the all-carbon di- -methane reaction. This system is one in which a central tetrahedral carbon atom is flanked by two vinyl groups. The fundamental reaction was discovered and reported in 1967 by Zimmerman and his coworkers147. A detailed account of this reaction and the closely related oxa-di- - and the aza-di- -methane rearrangements has been published recently148. This review gives the history of how and when the reaction was discovered and its developments in all its guises up to the present time. Others have reviewed other aspects of the reaction149. This section of this review will be devoted to the last decade of results.

The basic skeletal transformation exhibited by this system is shown in Scheme 4. Regardless of whether or not the reaction involves a singlet or a triplet, this scheme is a reasonable interpretation of the rearrangement. This shows the fundamentals of the reaction with the two alkene moieties separated from each other by the saturated carbon atom. The usual outcome of the irradiation is conversion to a vinyl cyclopropane, a 1,2- migration. Thus the two steps shown in Scheme 4, the formation of the 1,4-biradical A and then its transformation into the 1,3-biradical B, fundamentally brings about a 1,2- migration of a vinyl group. Calculations dealing with the outcome of the di- -methane rearrangement of 1,4-dienes have been reported150.

Ph

SCHEME 4

The reaction in its basic form is illustrated by the conversion of 274 into 275. This transformation shows the control exercised within the two biradicals A and B on the final outcome of the reaction151. Another typical di- -methane process, this time with electron-withdrawing substituents on one of the vinyl moieties, arises on acetophenonesensitized irradiation of the diene 276. This yields the cyclopropane 277 in 35% yield. The

SCHEME 6

B. Cyclic Systems

1. Benzotrienes

The benzotrienes 292 and 293, which have the di- -methane 1,4-diene system, are both photochemically and thermally reactive. Irradiation of 292 under either direct or sensitized conditions results in the formation of the semibullvalene 294 in 46% and 45% yield, respectively. This product arises by a di- -methane process in either the singlet or triplet excited states. The involvement of such a reaction has been proven by the use of suitable labelled compounds. Other products, isomeric benzocyclooctatetraenes and naphthalene, are also formed159. Like the methyl analogue the parent 293 is also photochemically reactive on both direct (wavelengths >280 nm) or sensitized (p-dimethylaminobenzophenone using wavelengths >345 nm) irradiation. The quantum yields for the formation of the semibullvalene 295 are 0.069 on direct irradiation and 0.082 for the sensitized approach. In this instance the authors160 have shown that the semibullvalene formed on direct irradiation is obtained by two reaction paths, a 1,2-shift process in competition with a di--methane rearrangement, in a ratio of 17 : 83. The triplet process leading to 295 occurs exclusively by the di- -methane reaction path. Semibullvalene products are also formed on irradiation of the cyano-substituted dienes 296. Direct irradiation of 296a gives the semibullvalene 297 in 55%. Sensitized irradiation is also effective and yields a mixture of the same semibullvalene 297 in 78% and the isomer 298 in 7%161. Direct or sensitized

R

R

irradiation of 296b affords the semibullvalene 299 as the main product (63% direct, 30% sensitized). Again, in this example the route to the semibullvalene is different, depending on which irradiation mode is employed. Labelling studies have provided evidence for this divergence of reaction path. Direct irradiation involves a 1,2-shift path while sensitization utilizes only the di- -methane path162. The corresponding semibullvalene 300 is obtained from irradiation of 296c but only in 5% yield. Again the dual paths to this have been demonstrated to be operative163. The ester-substituted derivatives, e.g. 301, are also photochemically reactive and follow the di- -methane rearrangement path to afford the semibullvalene 302164.

CO2Et

CO2Et

2. Benzonorbornadienes

The di- -methane rearrangement is also operative within the benzonorbornadiene system. In these cases the interaction within the excited state will involve the vinyl group and the benzo moiety. Considerable detail has been recorded for the rearrangement of such systems such as the triplet state reactivity of the derivatives 303. This work focused upon the influence of the bridgehead substituents on the outcome of the reactions and the control that these substituents have on the stability of the radicals formed on excitation. The result indicate that there is either bridgehead (intermediates A1 and B1) or vinylic control (intermediates A2 and B2) and the results are shown in Scheme 7165. Both acetone and acetophenone sensitization as well as direct irradiation bring about the cyclizations of 304. The triplet state processes are more efficient. The reactions encountered show some regiospecificity, as illustrated by the transformation of 304a–c quantitatively into 305. Only with 304d is a mixture of products 305d and 306d obtained. The influence of substituents within this system is also evidenced by the fact that some derivatives are unreactive or poorly reactive, as in 307166. Other studies have also examined the influence on the outcome of the reaction of the inclusion of substituents within the arene ring, in this instance a pyridine group. Again, the ratio of products obtained appears to be dependent upon the nature of the substituents and perhaps also on the stability that these exercise on the biradical intermediates (Schemes 8 and 9)167.

In more recent times interest has been shown in the effects of constrained environment on the outcome of such reactions. Some enantioselectivity in the product 308 has been reported following the irradiation of benzonorbornadiene 309 in a TlY zeolite. ( )- Ephedrine was used as the chiral inductor and sensitization brought about the reaction in 30 min. An ee of about 14% was obtained168.

3. Bicyclo[2.2.2]octadienes

The increase in ring size from the norbornadiene-type to bicyclo[2.2.2]octadiene systems appears not to affect the overall reaction outcome. Again the interaction involves

benzo/vinyl bridging. For example, the derivatives 310 can be effectively cyclized, with some evidence for regiospecificity, into the products 311 and 312. There is obviously

some control upon the reaction from substituents since the derivatives 310 (R1 D OMe, Cl, CN or CO2Me, R2 D H, CN or CO2Me) fail to cyclize166.

4. Benzobarrelenes

Benzobarrelenes are an important class of molecule where the di- -methane rearrangement is operative. Clearly, within this class there is a possibility that benzo –vinyl interactions can be in competition with vinyl –vinyl processes. The direct irradiation ( > 330 nm) of the benzobarrelene 313 in a variety of solvents (benzene, acetonitrile, methanol or hexane) affords two principal products 314 and 315 in a ratio of 1 : 1. The products are formed via a di- -methane process involving vinyl –vinyl bridging which