Acetylenes from cyclopropenes

The majority of preparative methods which have been used for obtaining cyclopropane derivatives involve carbene addition to an olefmic bond, if acetylenes are used in the reaction, cyclopropenes are obtained. Heteroatom-substituted or vinyl cydopropanes come from alkenyl bromides or enol acetates (A. de Meijere, 1979 E. J. Corey, 1975 B E. Wenkert, 1970 A). The carbenes needed for cyclopropane syntheses can be obtained in situ by a-elimination of hydrogen halides with strong bases (R. Kdstcr, 1971 E.J. Corey, 1975 B), by copper catalyzed decomposition of diazo compounds (E. Wenkert, 1970 A S.D. Burke, 1979 N.J. Turro, 1966), or by reductive elimination of iodine from gem-diiodides (J. Nishimura, 1969 D. Wen-disch, 1971 J.M. Denis, 1972 H.E. Simmons, 1973 C. Girard, 1974),... 

Ethyl diazopyruvate, under copper catalysis, reacts with alkynes to give furane-2-carboxylates rather than cyclopropenes u3) (Scheme 30). What looks like a [3 + 2] cycloaddition product of a ketocarbenoid, may actually have arisen from a primarily formed cyclopropene by subsequent copper-catalyzed ring enlargement. Such a sequence has been established for the reaction of diazoacetic esters with acetylenes in the presence of certain copper catalysts, but metallic copper, in these cases, was not able to bring about the ring enlargement14). Conversely, no cyclopropene derivative was detected in the diazopyruvate reaction. 

Diarylmethylenecyclopropa[6]naphthalenes 14, unlike their benzene parent counterparts which give cycloaddition reactions at the cyclopropene bridge bond [10a], react on the exo double bond in Diels-Alder cycloadditions (see Sect. 2.1.1) [10b]. The reactions of 14 with the highly electron-deficient acetylenic(phenyl)iodonium triflate 584 give products 586a and 587, which are believed to derive from unstable primary [2 + 2] cycloadducts 585 (Scheme 82) [10b],... 

Methylene cyclopropene (5), the simplest triafulvene, is predicted to be of very low stability. From different MO calculations5 it has been estimated to possess only minor resonance stabilization ranging to 1 j3. Its high index of free valency4 at the exocyclic carbon atom causes an extreme tendency to polymerize, a process favored additionally by release of strain. Thus it is not surprising that only one attempt to prepare this elusive C4H4-hydrocarbon can be found in the literature. Photolysis and flash vacuum pyrolysis of cis-l-methylene-cyclopropene-2,3-dicarboxylic anhydride (58), however, did not yield methylene cyclopropene, but only vinyl acetylene as its (formal) product of isomerization in addition to small amounts of acetylene and methyl acetylene65 ... 

A few examples of vinylogous methylene cyclopropenes are known. Thus, in an interesting reaction mode the spirohexadiene 93, prepared from dimethyl acetylene... 

From the electronic populations on the vinylic hydrogens, the acidity of vinylic C—H was estimated to be higher in cyclopropenone than in cyclopropene (0.684 e/ 0.776 e). This agrees with kinetic measurements of the H-D-exchange at n-propyl cyclopropenone23 which showed an acidity of the vinylic C—H even higher than that of the acetylenic C—H in the reference compound propargyl alcohol. 

A carbene has been generated at position 3 of the bislactim ether derived from cyclo(L-Val-Gly) via the lithio derivative and the diazo compound. The carbene has been trapped by an acetylene to provide a cyclopropene [88AG(E)433]. Hydrolysis with 0.1 N HC1 leads to the cyclopropene aminoacid esters (Scheme 70). 

Functionalized cyclopropenes are viable synthetic intermediates whose applications [99.100] extend to a wide variety of carbocyclic and heterocyclic systems. However, advances in the synthesis of cyclopropenes, particularly through Rh(II) carboxylate—catalyzed decomposition of diazo esters in the presence of alkynes [100-102], has made available an array of stable 3-cyclopropenecarboxylate esters. Previously, copper catalysts provided low to moderate yields of cyclopropenes in reactions of diazo esters with disubstituted acetylenes [103], but the higher temperatures required for these carbenoid reactions often led to thermal or catalytic ring opening and products derived from vinylcarbene intermediates (104-107). 

Cycloaddition of the carbene derived from 205 to bis(trimethylsilyl)acetylene yields the expected cyclopropene in low yield both photochemically (20%) and under catalysis by copper triflate at 80 °C (10-13%)119. The latter version of the reaction is accompanied by [3 + 2] cycloaddition of the diazo compound to the alkyne, and the photochemical route yields a by-product which obviously comes from carbenic C,H insertion at a SiMe3 group of the alkyne. 

Relevant examples of 1,2-dialkylcycloalkenes with which to test our conjecture about reaction 12 are disappointingly few. The simplest example of this class of compounds is 1,2-dimethylcyclopropene (24, n = 3, R1 = R2 = Me), and indeed, the requisite thermochemical data are available. Using the derived enthalpy of formation of 1,2-dimethylcyclopropene from Reference 56, we find this reaction to be 32 kJmol-1 endothermic. A posteriori, we are not surprised that this reaction is endothermic. After all, if it is part of the folklore of cyclopropanes that they are said to have olefinic character, then cyclopropenes are also said to have acetylenic character. Indeed, the related transalkylation reaction involving acetylenes... 

The first naphtho[a]cyclopropene 68d was also obtained by that route. 3H-indazole was proposed as an intermediate in this reaction 78>. The reaction proceeds equally well from the triplet state of 7. However with acetone light capture from the sensitizer may not have been complete. A trapping of the diradical intermediate 67 to give the known indene 69 by photolysing 7 in dimethyl-acetylene-dicarboxylate (ADC) afforded only a trace of 69. However the yield of 68a was reduced to 40%. Either trapping of 67 was not effective enough or ADC may have acted as quencher. Trapping with furan or cyclopentadiene was also not effective 78a). 

The most general methods for preparing seven- or eight-membered rings from enamines are by ring expansion of the cyclobutene, cyclobutanone or chlorocyclopro-pane adducts formed by cycloaddition of acetylene carboxylates, ketenes or chlor-ocarbenes, respectively, to enamines of cyclopentanone or cyclohexanone. These are two-carbon or one-carbon ring expansions. Three-carbon ring expansions can also be carried out by cycloaddition of activated cyclopropenes or cyclopropenones. 

New parameters of cyclopropene (155) have been calculated from existing MW data. A near-equilibrium structure has also been derived from scaled moments of iner-tia (Table 16). The lengths of the C—C single bond and the methylene C—H bond and H—C—H angle are similar to those in 1 (Table 1). The C=C bond is, however, considerably shorter than in ethene 1.337 (2) A, and (=)C—H is between C—H in ethene (Section II. A) and in acetylene, 1.0586 and 1.0547 A. Bond-length relations indicate that the methylene carbon in 155 uses approximately the same hybrid orbitals as 1, sp" and sp (Section II.A), to form bonds within the ring and to substituents, while the —CH= carbon in 155 is characterized by sp and sp hybrids, respectively ... 

Fatty acids with trans or non-methylene-interrupted unsaturation occur naturally or are formed during processing for example, vaccenic acid (18 1 Hr) and the conjugated linoleic acid (CLA) rumenic acid (18 2 9tllc) are found in dairy fats. Hydroxy, epoxy, cyclopropane, cyclopropene acetylenic, and methyl branched fatty acids are known, but only ricinoleic acid (12(/f)-hydroxy-9Z-octadecenoic acid) (2) from castor oil is used for oleochemical production. OUs containing vernolic acid (12(5),13(/ )-epoxy-9Z-octadecenoic acid) (3) have potential for industrial use. 

Cyclopropene-containing compounds are much rarer metabolites but a few well-characterized examples are known. It is likely they arise biogenetically from acetylenic precursors (themselves derived from olefins)" Sterculic acid (23)" has been isolated from... 

German chemists3 have used the method successfully for preparation of dichloro-cyclopropanes from olefins which yield little or no products when the dichlorocarbene is generated from chloroform and potassium r-butoxide. They also generated dibromo-carbene in the same way. Cyclopropenes are obtained in only low yields from acetylenes owing to side reactions. 

Table 1. Cyclopropene Derivatives from the Addition of Diazoalkanes to Acetylenes Followed by Photochemical Deazetization of the Intermediate 3//-Pyrazoles...

Diazopropane is a potential source of ge w-dimethyl groups. It undergoes 1,3-dipolar addition to acetylenes and allenes/ and the adducts can be photolyzed to give cyclopropenes or methylenecyclopropanes/ respectively. In certain cases the adducts from a-substituted acetylenes give good yields of allenes and conjugated dienes on photolysis. ... 

Activated Acetylenes. The unstable 1 2 adduct formed from the reaction of triphenylphosphine and dimethyl acetylenedicarboxylate at -50°C is now thought to have the cyclopropene structure (22) the... 

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