Cumulene derivative

Keywords cumulene derivative, [2+2]cycloaddition, [4]radialene tetracarboxylic acid... 

The FT-IR spectra of the polyynes acetylides is shown in Figure 18.3 where it is possible to appreciate the triple bonds stretching band at 2107 cm followed by another band at 1995-1977 cm In normal conditions the latter band can be attributed to allene or cumulene moieties and it is possible that the polyynes combination with copper causes partial isomerization on the chains due to the interaction with copper atoms. In any case, HPLC analysis has not revealed any allene or cumulene derivatives in the products of the carbon arc. Thereofore, the band at 1995-1977 cnC appears more a special feature of the copper acetylides. 

Such cumulenic derivatives cannot be obtained by isomerization of acetylenic precursors under catalytic conditions, since they are thermodynamically less stable than the acetylenes. Special conditions for the protonation of metallated acetylenic sulfides and metallated enyne amines are described in Refs. [7] and [106] and in Chap. IV, Exp. 19. 

The first book on the reactions of carbon cumulenes, treating the cycloaddition reactions of ketenes in depth, was written by Staudinger in 1912 Staudinger already realized that cycloaddition reactions of ketenes are common, and often ketenes were only isolated as cyclodimers. The cyclodimers of isocyanates became prominent in the development of polyurethanes in the IG Farben Laboratory in Leverkusen, Germany in the early 1930s and the cyclotrimerization of diisocyanates led to the development of polyisocyanurate foams, with thermal stability superior to rigid polyurethane foams in the 1960s. Today, polyisocyanurate foams are used in the insulation of the fuel tank of the space shuttle. Also, carbodiimide derived cellular plastics with improved thermal stability are of interest. In recent years, cumulene derived polymers became of interest as one-dimensional molecular wires. 

One of the most versatile methods for the synthesis of derivatives with the acetylene or cumulene system consists In deprotonatlon of the starting acetylene or cumulene and subsequent reaction of the anionic or organometal1ic intermediate with an electrophilic reagent. 

As indicated in the general scheme below, butatrienes are the first products from base-induced 1,4-elinination of hydrogen and a suitable leaving group. The butatriene in general very readily undergoes isomerization into enynes, if sufficiently "acidic" protons are available (see Chapter 11 in Ref. 3a). In aprotic media cumulenic ethers are fixed as their lithio derivatives if an excess of alkyllithium is applied... 

The intemiediate (25) reacts with ketones (R 2 0) to form cumulenes RC(CH2)=C=CR2. The indenyl derivative reacts similarly. 

A derivative of cyclopentyne has been trapped in a matrix. Although cycloheptyne and cyclohexyne have not been isolated at room temperatures, Pt(0) complexes of these compounds have been prepared and are stable." The smallest cyclic allene" so far isolated is l-/err-butyl-l,2-cyclooctadiene 107." The parent 1,2-cyclooctadiene has not been isolated. It has been shown to exist transiently, but rapidly dimerizes." " The presence of the rert-butyl group apparently prevents this. The transient existence of 1,2-cycloheptadiene has also been shown," and both 1,2-cyclooctadiene and 1,2-cycloheptadiene have been isolated in platinum complexes." 1,2-Cyclohexadiene has been trapped at low temperatures, and its structure has been proved by spectral smdies." Cyclic allenes in general are less strained than their acetylenic isomers." The cyclic cumulene 1,2,3-cyclononatriene has also been synthesized and is reasonably stable in solution at room temperature in the absence of air." ... 

The compound 251 decarbonylates on photolysis to bis(4-hydroxyaryl) acetylene 253, which is easily oxidized to the quinonoid cumulene 254. This is also obtained by thermal decarbonylation of the product of oxidation of cyclopropenone 251, the diquinocyclopropanone 252. Likewise, the blue derivative of 3-radialene 256 (a phenylogue of triketo cyclopropane) is formed from tris-(4-hydroxyaryl) cyclopropenium cation 255 by oxidation34. ... 

Radialenes represent the biggest and best known subset of the radialene family this is not surprising in view of the fact that more methods to prepare them exist than for any other class of radialenes. The major strategies are the transformation of appropriate cyclobutane derivatives, the thermal or Ni(0)-catalyzed cyclodimerization of butatrienes or higher cumulenes and the cyclotetramerization of (l-bromo-l-alkenyl)cuprates. 

The cyclodimerization of 82 to 83 is an example of a Ni(0)-mediated synthesis of [4]radialenes from [n]cumulenes. Applications of this method to butatriene derivatives 9050,63, 9164 and 9365,66 are shown in Scheme 10. The usefulness of Ni(0) catalysis for this transformation was first demonstrated by West and coworkers63 and later explored in detail by Iyoda and coworkers42,54,67. In some cases, Ni(0) catalysis improves the... 

In order to complete the list of carbon oxides C =0 (n = 1-9) it should be mentioned that, as it was already discussed for C5O, also the higher members C7O, C80, and C9O have not been yet isolated in a matrix, but they could be generated by Endo et al.134,135 in the gas phase by an electric discharge in a mixture of C3O2 and argon. The reaction products were analyzed by rotational spectra, from which the linear cumulenic structure and the bond lengths were derived. 

Pyrrolizin-3-ones may also be obtained by FVP of 3-(pyrrol-2-yl)propenoate esters such as 62, 69, and 74. Also, benzo-annulated pyrrolizinone 17 was obtained by FVP of 2-(tf-methoxycarbonyl phenyl (pyrrole <1999J(P1)2047>. FVP of alcohols 77, 78, and 79 led to 3//-pyrrolyzine derivatives 1, 192, and 193, respectively, in good yields (66-95%). These transformations proceed by elimination of water and subsequent electrocyclization of the in situ-generated cumulene (Scheme 44) <1999J(P1)2049>. 

If allenes bear a potential leaving group in the a-position to the cumulene system, they are very attractive substrates for palladium-catalyzed substitutions. Examples are a-allenic acetates and particularly a-allenic phosphates, which react under palladium(O) catalysis with carbanions derived from /3-diesters, /i-keto esters, a-phenylsulfonyl esters and glycine ester derivatives. They lead to /3-functionalized allenes such as 86, 89 and 93 (Eqs. 14.9-14.11) [45 18]. 

Knoke and de Meijere [60] recently developed a highly flexible domino Heck-Diels-Alder reaction of a symmetrically substituted cumulene 125, which also involves cross-couplings of an allene at the central position. Both aryl and hetaryl halides react efficiently with l,3-dicyclopropyl-l,2-propadiene (125) and furnish 1,3,5-hexatriene derivatives 126 as intermediates, which are usually trapped by acceptor-substituted olefins in a subsequent cycloaddition, providing adducts 127a/b in moderate to good overall yields (Scheme 14.30). 

It is interesting to mention the cyclizations of allene systems which are accompanied by rearrangements. Protonation of the bis-cumulene 74 by 5% H2SO4 in aqueous acetone produces the adamantane derivative 75 in 95% yield (equation 28)43. 

Addition of silyl radicals to cumulenes and their isoelectronic derivatives has mainly been studied by EPR spectroscopy. The adducts of MesSi radical with the two substituted allenes 54 and 55 have been recorded [73,74]. The attack occurs at the central atom affording unconjugated allyl-type radicals. In particular the adduct radical with 55 has been described as a very persistent perpendicular allyl radical [74]. 

Cp=Cy bond of indenyl-allenylidene complexes 30 which leads to the stereoselective formation of cationic amino-allenylidenes 31. When R = Ph, complexes 31 can be transformed into the secondary derivatives 32 via treatment with LiBHEts and subsequent purification on sUica-gel column. Further insertions of MeC=CNEt2 into 32 allow the preparation of polyunsaturated cumulene chains (related insertion reactions will be discussed in the reactivity section). 

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