Propadiene, the simplest allene, is also known as allene
Inorganic chemistry,allenes areorganic compounds in which onecarbon atom hasdouble bonds with each of its two adjacent carbon atoms (R2C=C=CR2, where R isH or someorganyl group).[1] Allenes are classified ascumulated dienes. The parent compound of this class ispropadiene (H2C=C=CH2), which is itself also calledallene. A group of the structureR2C=C=CR− is calledallenyl, while a substituent attached to an allene is referred to as anallenic substituent (R is H or some alkyl group). In analogy toallylic andpropargylic, a substituent attached to a saturated carbon α (i.e., directly adjacent) to an allene is referred to as anallenylic substituent. While allenes have two consecutive ('cumulated') double bonds, compounds with three or more cumulated double bonds are calledcumulenes.
For many years, allenes were viewed as curiosities but thought to be synthetically useless and difficult to prepare and to work with.[2][3] Reportedly,[4] the first synthesis of an allene,glutinic acid, was performed in an attempt to prove the non-existence of this class of compounds.[5][6] The situation began to change in the 1950s, and more than 300 papers on allenes have been published in 2012 alone.[7] These compounds are not just interesting intermediates but synthetically valuable targets themselves; for example, over 150 natural products are known with an allene or cumulene fragment.[4]
The central carbon atom of allenes forms twosigma bonds and twopi bonds. The central carbon atom issp-hybridized, and the two terminal carbon atoms aresp2-hybridized. The bond angle formed by the three carbon atoms is 180°, indicating linear geometry for the central carbon atom. The two terminal carbon atoms are planar, and these planes are twisted 90° from each other. The structure can also be viewed as an "extended tetrahedral" with a similar shape tomethane, an analogy that is continued into the stereochemical analysis of certain derivative molecules.
The symmetry and isomerism of allenes has long fascinated organic chemists.[8] For allenes with four identical substituents, there exist two twofold axes of rotation through the central carbon atom, inclined at 45° to the CH2 planes at either end of the molecule. The molecule can thus be thought of as a two-bladedpropeller. A third twofold axis of rotation passes through the C=C=C bonds, and there is a mirror plane passing through both CH2 planes. Thus this class of molecules belong to the D2dpoint group. Because of the symmetry, an unsubstituted allene has no netdipole moment, that is, it is a non-polar molecule.
R andS configurations are determined by precedences of the groups attached to the axial section of the molecule when viewed along that axis. The front plane is given higher priority over the other and the final assignment is given from priority 2 to 3 (i.e. the relationship between the two planes).
An allene with two different substituents on each of the two carbon atoms will bechiral because there will no longer be any mirror planes. The chirality of these types of allenes was first predicted in 1875 byJacobus Henricus van 't Hoff, but not proven experimentally until 1935.[9] WhereA has a greater priority thanB according to theCahn–Ingold–Prelog priority rules, the configuration of theaxial chirality can be determined by considering the substituents on the front atom followed by the back atom when viewed along the allene axis. For the back atom, only the group of higher priority need be considered.
Chiral allenes have been recently used as building blocks in the construction of organic materials with exceptional chiroptical properties.[10] There are a few examples of drug molecule having an allene system in their structure.[11] Mycomycin, an antibiotic with tuberculostatic properties,[12] is a typical example. This drug exhibits enantiomerism due to the presence of a suitably substituted allene system.
Although the semi-localized textbookσ-π separation model describes the bonding of allene using a pair of localized orthogonal π orbitals, the full molecular orbital description of the bonding is more subtle. The symmetry-correct doubly-degenerate HOMOs of allene (adapted to the D2d point group) can either be represented by a pair of orthogonal MOsor as twisted helical linear combinations of these orthogonal MOs. The symmetry of the system and the degeneracy of these orbitals imply that both descriptions are correct (in the same way that there are infinitely many ways to depict the doubly-degenerate HOMOs and LUMOs of benzene that correspond to different choices of eigenfunctions in a two-dimensional eigenspace). However, this degeneracy is lifted in substituted allenes, and the helical picture becomes the only symmetry-correct description for the HOMO and HOMO–1 of the C2-symmetric1,3-dimethylallene [de].[13][14] This qualitative MO description extends to higher odd-carbon cumulenes (e.g., 1,2,3,4-pentatetraene).
Allenes differ considerably from other alkenes in terms of their chemical properties. Compared to isolated and conjugated dienes, they are considerably less stable: comparing the isomericpentadienes, the allenic 1,2-pentadiene has a heat of formation of 33.6 kcal/mol, compared to 18.1 kcal/mol for (E)-1,3-pentadiene and 25.4 kcal/mol for the isolated 1,4-pentadiene.[15]
The C–H bonds of allenes are considerably weaker and more acidic compared to typical vinylic C–H bonds: thebond dissociation energy is 87.7 kcal/mol (compared to 111 kcal/mol in ethylene), while thegas-phase acidity is 381 kcal/mol (compared to 409 kcal/mol for ethylene[16]), making it slightly more acidic than the propargylic C–H bond of propyne (382 kcal/mol).
The13C NMR spectrum of allenes is characterized by the signal of the sp-hybridized carbon atom, resonating at a characteristic 200-220 ppm. In contrast, the sp2-hybridized carbon atoms resonate around 80 ppm in a region typical for alkyne andnitrile carbon atoms, while the protons of a CH2 group of a terminal allene resonate at around 4.5 ppm – somewhat upfield of a typical vinylic proton.[17]
Allenes possess a rich cycloaddition chemistry, including both [4+2] and [2+2] modes of addition,[18][19] as well as undergoing formal cycloaddition processes catalyzed by transition metals.[20][21] Allenes also serve as substrates for transition metal catalyzed hydrofunctionalization reactions.[22][23][24]
Much like acetylenes, electron-poor allenes are unstable. Tetrachloroallene polymerizes quantitatively to perchloro(1,2-dimethylenecyclobutane) at −50 °C.[25]
Cyclic allenes with fewer than 10 ring atoms arestrained. Those with fewer than 8 atoms generally only form unstablearyne-like intermediates.[26][27]: 6–7 The latter are sometimes stabilized bydiradical orylidic resonance structures.[27]: 14–15 [28]
Although allenes often require specialized syntheses, the parent allene,propadiene is produced industrially on a large scale as an equilibrium mixture withpropyne:
This mixture, known asMAPP gas, is commercially available. At 298 K, the ΔG° of this reaction is –1.9 kcal/mol, corresponding toKeq = 24.7.[29]
The first allene to be synthesized waspenta-2,3-dienedioic acid, which was prepared by Burton and Pechmann in 1887. However, the structure was only correctly identified in 1954.[30]
Laboratory methods for the formation of allenes include:
One of the older methods is the Skattebøl rearrangement[48][52][53] (also called the Doering–Moore–Skattebøl or Doering–LaFlamme[54][55] rearrangement), in which a gem-dihalocyclopropane3 is treated with an organolithium compound (or dissolving metal) and the presumed intermediate rearranges into an allene either directly or via carbene-like species. Notably, even strained allenes can be generated by this procedure.[56] Modifications involving leaving groups of different nature are also known.[48] Arguably, the most convenient modern method of allene synthesis is bysigmatropic rearrangement ofpropargylic substrates.[49][50][51] Johnson–Claisen[51] and Ireland–Claisen[57] rearrangements of ketene acetals4 have been used a number of times to prepare allenic esters and acids. Reactions ofvinyl ethers5 (the Saucy–Marbet rearrangement) give allene aldehydes,[58] while propargylic sulfenates6 give allene sulfoxides.[59][60] Allenes can also be prepared bynucleophilic substitution in9 and10 (nucleophile Nu− can be a hydride anion),1,2-elimination from8, proton transfer in7, and other, less general, methods.[49][50]
The reactivity of substituted allenes has been well explored.[19][42][62][63]
The twoπ-bonds are located at the 90° angle to each other, and thus require a reagent to approach from somewhat different directions. With an appropriate substitution pattern, allenes exhibit axial chirality as predicted by Van 't Hoff as early as 1875.[64][63] Protonation of allenes gives cations11 that undergo further transformations.[65] Reactions with soft electrophiles (e.g. Br+) deliver positively chargedonium ions13.[66] Transition-metal-catalysed reactions proceed via allylic intermediates15 and have attracted significant interest in recent years.[67][68] Numerous cycloadditions are also known, including [4+2]-, (2+1)-, and [2+2]-variants, which deliver, e.g.,12,14, and16, respectively.[19][69][70][71]
Numerous natural products contain the allene functional group. Noteworthy are the pigmentsfucoxanthin andperidinin. Little is known about the biosynthesis, although it is conjectured that they are often generated from alkyne precursors.[72]
Allenes serve as ligands inorganometallic chemistry. A typical complex is Pt(η2-allene)(PPh3)2. Ni(0) reagents catalyze the cyclooligomerization of allene.[73] Using a suitable catalyst (e.g.Wilkinson's catalyst), it is possible to reduce just one of the double bonds of an allene.[74]
Many rings or ring systems are known by semisystematic names that assume a maximum number of noncumulative bonds. To unambiguously specify derivatives that include cumulated bonds (and hence fewer hydrogen atoms than would be expected from the skeleton), a lowercase delta may be used with a subscript indicating the number of cumulated double bonds from that atom, e.g. 8δ2-benzocyclononene. This may be combined with the λ-convention for specifying nonstandard valency states, e.g. 2λ4δ2,5λ4δ2-thieno[3,4-c]thiophene.[75]
^Pretsch, Ernö; Bühlmann, Philippe; Badertscher, M. (2009).Structure determination of organic compounds : tables of spectral data (Fourth, Revised and Enlarged ed.). Berlin: Springer.ISBN978-3-540-93810-1.OCLC405547697.
^Lang, Robert W.; Hansen, Hans-Jürgen (1980). "Eine einfache Allencarbonsäureester-Synthese mittels der Wittig-Reaktion" [A simple synthesis of allene carboxylic acid esters by means of the Wittig reaction].Helv. Chim. Acta.63 (2):438–455.doi:10.1002/hlca.19800630215.
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^Brandsma, L.; Verkruijsse, H.D. (2004).Synthesis of acetylenes, allenes and cumulenes : methods and techniques (1st ed.). Amsterdam: Elsevier.ISBN978-0-12-125751-4.OCLC162570992.
^Kurti, Laszlo; Czako, Barbara (2005).Strategic Applications of Named Reactions in Organic Synthesis : Background and Detailed Mechanisms. Burlington: Elsevier Science. p. 758.ISBN978-0-08-057541-4.OCLC850164343.
^Van ’t Hoff, J. H.La Chimie dans l’Espace; P.M. Bazendijk, 1875; p. 43.
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^Krause, Norbert; Hoffmann-Röder, Anja (2004). "18. Allenic Natural Products and Pharmaceuticals". In Krause, Norbert; Hashmi, A. Stephen K. (eds.).Modern Allene Chemistry. pp. 997–1040.doi:10.1002/9783527619573.ch18.ISBN9783527619573.
^Otsuka, Sei; Nakamura, Akira "Acetylene and allene complexes: their implication in homogeneous catalysis" Advances in Organometallic Chemistry 1976, volume 14, pp. 245-83.doi:10.1016/S0065-3055(08)60654-1.
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