Cyclobutene-diene

Simple cyclobutanes do not readily undergo such reactions, but cyclobutenes do. Ben-zocyclobutene derivatives tend to open to give extremely reactive dienes, namely ortho-c]uin(xlimethanes (examples of syntheses see on p. 280, 281, and 297). Benzocyclobutenes and related compounds are obtained by high-temperature elimination reactions of bicyclic benzene derivatives such as 3-isochromanone (C.W. Spangler, 1973, 1976, 1977), or more conveniently in the laboratory, by Diels-Alder reactions (R.P. Thummel, 1974) or by cycliza-tions of silylated acetylenes with 1,5-hexadiynes in the presence of (cyclopentadienyl)dicarbo-nylcobalt (W.G, Aalbersberg, 1975 R.P. Thummel, 1980). 

Fluorinated cyclobutanes and cyclobutenes are relatively easy to prepare because of the propensity of many gem-difluoroolefins to thermally cyclodimerize and cycloadd to alkenes and alkynes. Even with dienes, fluoroolefins commonly prefer to form cyclobutane rather than six-membered-ring Diels-Alder adducts. Tetrafluoroethylene, chlorotrifluoroethylene, and l,l-dichloro-2,2-difluoroethyl-ene are especially reactive in this context. Most evidence favors a stepwise diradical or, less often, a dipolar mechanism for [2+2] cycloadditions of fluoroalkenes [S5, (5], although arguments for a symmetry-allowed, concerted [2j-t-2J process persist [87], The scope, characteristic features, and mechanistic studies of fluoroolefin... 

Figure 15.20 Two possible modes of closing a diene to cyclobutene...

The ring closure of a diene to a cyclobutene can occur with rotation of the two termini in the same conrotatory) or opposite disrotatory) directions. For suitable substituted compounds, these two reaction modes lead to products with different stereochemistry. 

The best way to understand how orbital symmetry affects pericyclic reactions is to look at some examples. Let s look first at a group of polyene rearrangements called electrocyclic reactions. An electrocyclic reaction is a pericyclic process that involves the cycli/ation of a conjugated polyene. One 7r bond is broken, the other 7t bonds change position, a new cr bond is formed, and a cyclic compound results. For example, a conjugated triene can be converted into a cyclohexa-diene, and a conjugated diene can be converted into a cyclobutene. 

Both reactions are reversible, and the position of the equilibrium depends on the specific case. In general, the triene cyclohexadiene equilibrium favors the cyclic product, whereas the diene cyclobutene equilibrium favors the unstrained open-chain product. 

Compound 6 is a pivotal intermediate in Schreiber s synthesis. It was hoped that the conspicuous and strained bridgehead cyclobutene substructure in 6 would undergo a conrotatory electrocyclic ring opening upon thermolysis to give an isomeric 1,3-diene (8, Scheme 1). In the event, when a solution of cyclobutene 6 in toluene is confined to a sealed tube and heated to 180°C for 12 h, a stereoisomeric mixture of 1,3-dienes 7 and 8 is produced in an excellent yield of 95% (7 8 ca. 5 1). Finally, irradiation of the 5 1 mixture of cis-7 and trans-8, or of each independently, establishes a photostationary state in which the desired trans isomer 8 predominates (8 7 ca. 10 1). 

Cyclic dienes and polyenes, monocyclic as well as bicyclic, can be metathesized in the same way as cyclic monoenes. As expected, cyclobutene 27), 1,5-cyclooctadiene, and 1,5,9-cyclododecatriene 28) yield the same polyalkenamer, in this case polybutenamer (1,4-polybutadiene), since these reactants consist of the same base units, i.e.—(CH2)2CH==CH— ... 

Crotonaldehyde, hydrogenation of, 43-48 Cubane, isomerization of, 148 Cyclic dienes, metathesis of, 135 Cyclic polyenes, metathesis of, 135 Cycloalkenes, metathesis of, 134-136 kinetic model, 164 ring-opening polymerization, 143 stereoselectivity, 158-160 transalkylation, 142-144 transalkylidenation, 142-144 Cyclobutane configuration, 147 geometry of, 145, 146 Cyclobutene, metathesis of, 135 1,5,9-Cyclododecatriene, metathesis of, 135... 

Intermolecular [4C+2S] cycloaddition reactions where the diene moiety is contained in the carbene complex are less frequent than the [4S+2C] cycloadditions summarised in the previous section. However, 2-butadienylcarbene complexes, generated by a [2+2]/cyclobutene ring opening sequence, undergo Diels-Alder reactions with typical dienophiles [34,35] (Scheme 59). Also, Wulff et al. have described the application of pyranylidene complexes, obtained by a [3+3] cycloaddition reaction (see Sect. 2.8.1), in the inverse-electron-demand Diels-Alder reaction with enol ethers and enamines [87a]. Later, this strategy was applied to the synthesis of steroid-like ring skeletons [87b] (Scheme 59). 

A cyclobutene ROCM sequence was also used in a synthesis of racemic sporochnol (410), a naturally occurring feeding deterrent toward herbivorous fish (Scheme 80) [170]. Exposing cyclobutene 406 (0.01 M in boiling 1,2-dichloroethane) in the presence of ethylene to second-generation catalyst C (8 mol%) led to 1,5-diene 407 in 73% yield, along with 9% of the homodimer derived from 407 by involving the less hindered double bond. Site-selective hy-... 

Most cyclic and acyclic 1,3-dienes, such as cyclopentadiene, undergo photochemical ring-closure to cyclobutenes. Cyclopentadiene-<5-d, cyclopentadiene-d, 2-methyleyclopentadiene,1 and 1-methylcyclo-pentadiene11 have been converted to the corresponding bicyelo-[2.1.0]pent-2-ene derivatives. 

The reverse reaction is also conrotatory. In contrast, the photochemical cyclobutene 1,3-diene interconversion is disrotatory in either direction." On the other hand, the... 

This time it is conrotatory movement that results in a bonding situation, and formation of the trans dimethylcyclobutene (18). For the photochemical interconversion (which tends to lie over in favour of the cyclobutene), irradiation of the diene will result in the promotion of an electron into the orbital of next higher energy level, i.e. 3, and the HOMO to be considered now therefore becomes i/r3 (23) ... 

Thiopyranopyrrolizines can be prepared readily from the enamine 170 upon treatment with DMAD. Alternatively, heating of the thiacyclooctadiene derivative 171 in methanol gives the same tricycle 172, but this time as a 5 2 mixture with the (Z,E)-isomer of the precursor 171. These reactions probably involve the the intermediacy of an unstable cyclobutene and/or a zwitterionic diene, as shown in Scheme 51 <1984JA1341>. 

Palladocyclopentadiene reagent promotes [2 + 2]-cycloaddition of suitably positioned enynes to form cyclobutenes which undergo symmetry allowed ring opening to form 1,3-dienes with a bridgehead double bond (equation 149)264. 

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