Bicyclo octenone cycloaddition reactions

Recently, the reaction of masked ortho-benzoquinone [92] with C60 was tested [93]. The [4+2] cycloaddition reaction of such electron-deficient dienes with fullerenes resulted in the formation of highly functionalized bicyclo [2.2.2] octenone-fused fullerenes. The reactants were generated in situ by the oxidation of the readily available 2-methoxy phenols with hypervalent iodine agents. For the several different masked ortho-benzoquinones that were tested, it was found that the yield of the cycloadducts depends on the nature of the starting materials and the reaction conditions. Other Diels-Alder reactions of such electron-deficient dienes with electron-poor fullerenes involved tropones [94], 1,3-butadienes substituted with electron-withdrawing groups [95], and 2-pyrone [96]. 

Another early success of the (TpRe(CO)(MeIm) fragment was the promotion of Diels-Alder cycloaddition reactions with benzene and anisole. Complex 101 [TpRe(CO)(MeIm)( 2-benzene)] undergoes an endo-selective Diels-Alder reaction with N-methylmaleimide to afford the bound bicyclo[2.2.2]octadiene complex 102 in 65 % yield (Scheme 12) [40]. Oxidation of 102 yields the bicyclo[2.2.2]octadiene 103 and/or the bicyclo[2.2.2]octenone 104 depending upon the choice of oxidation conditions. 

The (1S,5R)-2-oxabicydo-octenone (see Fig. 5) is formed with 96% ee from one ketone enantiomer of racemic bicyclo[3.2.0]hept-2-en-6-one, which is synthesized in a cycloaddition reaction from cyclopentadiene and dichloroacetylchloride with subsequent Zn-reduction. The key limitation to the biocatalytic Baeyer-Villiger process is product inhibition [26]. In order to overcome product inhibition problems, in situ product removal was required. 

Recognizing that intermediates in the [5 + 2]-reaction of VCPs and 7r-systems could be trapped with other components, Wender and co-workers reported a three-component [5 + 2 + l]-cycloaddition involving VCPs, alkynes, and CO that provide efficient access to densely functionalized bicyclo[3.3.0]octenones via a cyclooctadienone intermediate (Scheme 55).129 This reaction converts three commercially available materials to bicyclic products and creates two stereocenters and four C-C bonds. 

MOBs reactive with cyclohexa-2,4-dienones undergo Diels-Alder cycloadditions with [60]fullerene to produce hitherto unknown, stable, and highly functionalized bicyclo-[2.2.2]-octenone derivatives. In light of the mild conditions and considerable generality, these reactions are certainly noteworthy... 

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