Cycloheptatriene cycloaddition

The following compounds have been obtained from thiete 1,1-dioxide Substituted cycloheptatrienes, benzyl o-toluenethiosulfinate, pyrazoles, - naphthothiete 1,1-dioxides, and 3-subst1tuted thietane 1,1-dioxides.It is a dienophile in Diels-Alder reactions and undergoes cycloadditions with enamines, dienamines, and ynamines. Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH2=CHCH=SQ2). which undergoes cyclo-additions to strained olefinic double bonds, reacts with phenol to give allyl sulfonate derivatives or cyclizes unimolecularly to give an unsaturated sultene. - Platinum and iron complexes of thiete 1,1-dioxide have been reported. 

An interesting cycloheptatriene (182) synthesis has been described using thiophene 1, 1-dioxides (180) and cyclopropenes 181 (equation 121)ns. Concerted [4 + 2]cycloaddition and subsequent cheletropic extrusion of sulfur dioxide are suggested by the second-order kinetics (first in each reactant), and by the large negative activation entropy. 

The reaction of alkenylcarbene complexes and alkynes in the presence of Ni(0) leads to cycloheptatriene derivatives in a process which can be considered as a [3C+2S+2S] cycloaddition reaction [125]. As shown in Scheme 77, two molecules of the alkyne and one molecule of the carbene complex are involved in the formation of the cycloheptatriene. This reaction is supposed to proceed through the initial formation of a nickel alkenylcarbene complex. A subsequent double regioselective alkyne insertion produces a new nickel carbene complex, which evolves by an intramolecular cycloprop anation reaction to form a nor-caradiene intermediate. These species easily isomerise to the observed cycloheptatriene derivatives (Scheme 77). 

It has been shown how alkenylcarbene complexes participate in nickel(0)-me-diated [3C+2S+2S] cycloaddition reactions to give cycloheptatriene derivatives (see Sect. 3.3). However, the analogous reaction performed with alkyl- or aryl-carbene complexes leads to similar cycloheptatriene derivatives, but in this case the process can be considered a [2S+2S+2S+1C] cycloaddition reaction as three molecules of the alkyne and one molecule of the carbene complex are incorporated into the structure of the final product [125] (Scheme 82). The mechanism of this transformation is similar to that described in Scheme 77 for the [3C+2S+2S] cycloaddition reactions. 

Alkoxycarbene complexes with unsaturation in the alkyl side chain rather than the alkoxy chain underwent similar intramolecular photoreactions (Eqs. 10 and 11) [60]. Cyclopropyl carbene complexes underwent a facile vinyl-cyclopropane rearrangement, presumably from the metal-bound ketene intermediate (Eqs. 12 and 13) [61]. A cycloheptatriene carbene complex underwent a related [6+2] cycloaddition (Eq. 14) [62]. 

The reaction of troponephenylhydrazone with carbon disulphide afforded the bicyclic thiazole (37) in quantitative yield. iV-methoxytroponimine when treated with phenylisothiocyanate afforded a mixture of cycloheptatriene derivatives (38a) and (38b). Both of these reactions proceed via an [8+2] cycloaddition <95H1675>. 

The reaction of hexafluoroacetone azine with cycloheptatriene at 70 °C provides after 8 days a mixture containing 28% of unchanged azine 290 and products formed by three distinct mechanistic pathways, that is, criss-cross cycloaddition product 294, a bis-ene adduct 295 and its oxidation product 296, and [3+6] cycloaddition leading to diaziridine 297, in the ratio 15 38 7 (Scheme 40) <1995JFC(73)203>. 

Some features are characteristic of reactions of nitrile oxides with 2,4,6-cyclo-hep tatrien-l-imines (8-azaheptafulvenes). 1,3-Dipolar cycloaddition to the C=N double bond of N-aryl-2,4,6-cycloheptatrien-l-imines 142 (R = Ar), affording... 

The [6 + 3]-cycloaddition between (cycloheptatriene)chromium(O) tricarbonyl 135 and isocyanate or ketene occurs under photo-irradiation conditions, for example, bicyclo[4.2.1]nonane-type adduct 136 was obtained in moderate yield (Equation (22)).237 238... 

The metal-mediated and metal-catalyzed [6 + 2]- and [6 + 4]-cycloaddition reactions, pioneered by Pettit and co-workers105 106 and Kreiter and co-workers,107 respectively, involve the cycloaddition of metal-complexed cyclic trienes with 7r-systems such as alkenes, alkynes, and dienes. The [6 + 2]-reactions produce bicyclo[4.2.1]nonadiene derivatives and the [6 + 4]-reactions produce bicyclo[4.4.1]undecatrienes (Scheme 32). Trienes complexed to chromium, which can be prepared on large scale (40 g) as reported by Rigby and co-workers,108 react with 7r-systems upon thermolysis or irradiation.109-111 Chromium and iron-catalyzed [6 + 2]-reactions of cycloheptatrienes and disubstituted alkynes... 

Although disubstituted alkynes are used successfully as two-carbon components in chromium-mediated and -catalyzed [6 + 2]-reactions, the use of terminal alkynes produces a [6 + 2 + 2]-reaction (Section 10.13.3.7). Buono and co-workers have discovered that when a cobalt catalyst is employed, several monosubstituted alkynes can be used in [6 + 2]-cycloadditions with cycloheptatriene (Scheme 35). The use of a chiral BINOL-phosphoramidite cobalt complex affords an enantioselective [6 + 2]-cycloaddition reaction (Equation (18)).121... 

In addition to cycloheptatriene, cyclooctatriene and cyclooctatetraene systems can be used as six-carbon components in the [6 + 2]-cycloaddition with 7t-systems (Scheme 36). Interestingly, in these cases, dienes react exclusively... 

The palladium-catalyzed trimethylenemethane reaction with tropanones was reported in 1987 by Trost and Seoane and is the first example of a [6 + 3]-cycloaddition.130 Chromium-mediated [6 + 3]-cycloadditions of two types have been described-one in which the chromium complex activates the six-carbon component and one in which the chromium complex activates the three-atom component. An example of the first type involves the reaction of a cycloheptatriene-Cr(CO)3 complex with azirines to give cyclic imines in moderate yields (Scheme 40).131... 

In addition to 534, further [4+2]-cycloadducts of 5 were prepared by using 1,3-dienes, some of which are well known as trapping reagents of short-lived cyclic allenes and cycloalkynes. Further, cycloadditions could be achieved with tropone and several 2-substituted tropones, 8,8-dicyanoheptafulvene, 1,3,5-cycloheptatriene and a few of its 7-substituted derivatives. The products of these reactions are represented in Scheme 6.108. 

Cycloheptatriene represents a challenging substrate for cycloaddition. It can react either in a [2 + 4 ]- or [2 + 6]-cycloaddition to yield isomeric endoperoxides 53 and 54, respectively (Scheme 9.8). Moreover, it may give a 1,2-dioxetane (55) in a [2 + 2] process. Norcaradiene, its valence isomer, may also yield a [2 + 4] adduct (56). All four products were detected in the transformation of the nonsubstituted molecule.421,422... 

No evidence for Dewar-isobenzofuran 150 was obtained, however a small amount of o-phthalaldehyde detected in the mixture may point to 150 as an intermediate. The photoreactions of 1,3-DIBF with cycloheptatriene (74TL343 75JA355 80AHC135) have been reinvestigated (83CB618).With anthracene a [774 + 7t4] cycloadduct (56%, mp 173°C) is obtained (83CB618). A thermal cycloaddition across the 4,7-position of an isobenzofuran has been reported previously (78JHC793). 

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