Dendralene

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A dendralene is a discrete acyclic cross-conjugated polyene. [1] [2] [3] The simplest dendralene is buta-1,3-diene (1) or [2]dendralene followed by [3]dendralene (2), [4]dendralene (3) and [5]dendralene (4) and so forth. [2]dendralene (butadiene) is the only one not cross-conjugated.

Contents

Dendralenes general.svg

The name dendralene is pulled together from the words dendrimer, linear and alkene. The higher dendralenes are of scientific interest because they open up a large array of new organic compounds from a relatively simple precursor especially by Diels-Alder chemistry. Their cyclic counterparts are aptly called radialenes.

Synthesis

Vinylbutadiene ([3]dendralene) was first prepared in 1955 by pyrolysis of a triacetate: [4] [5]

Vinyl butadiene synthesis Baily 1955.svg

This compound reacts with two equivalents of maleic anhydride in a tandem DA reaction: [6]

Reaction vinylbutadiene maleic anhydride.svg

With benzoquinone the reaction product was a linear polymer.

Several syntheses of substituted [3]dendralenes have been reported, one via an allene, [7] one via a Horner–Wadsworth–Emmons reaction, [8] one via a cross-coupling reaction [9] and one from an allylic carbonate. [10]

One synthetic route to [4]dendralene starts from chloroprene. [11] This compound is converted to a Grignard reagent by action of magnesium metal which is then reacted with copper(I) chloride to an organocopper intermediate which is in turn dimerized using copper(II) chloride in an oxidative coupling reaction to give the butadiene dimer called [4]dendralene.

4-dendralene.svg

The gas-phase molecular structure of [4]dendralene has been reported [12]

The [8]-dendralene compound was reported in 2009: [13]

8-dendralene.svg

in a successive Kumada–Tamao–Corriu coupling and Negishi coupling.

A series of [9] to [12]-dendralenes has been reported in 2016 [14]

Properties

Even-membered dendralenes (e.g. [6]dendralene, [8]dendralene) tend to behave as chains of decoupled and isolated diene units. The ultraviolet absorption maxima equal that of butadiene itself. The dendralenes with an odd number of alkene units are more reactive due to the presence of favorable s-cis diene conformations and Diels-Alder reactions take place more easily with a preference for the termini.

Reactions

With simple dienophiles, dendralenes can give quick access to complex molecules in Diels-Alder reactions. Several reaction schemes have been reported [11] [15] [16] [17] [18] [19] [20] [21] [22]

[4]dendralene shows a tandem Diels-Alder reaction with the dienophile N-methyl-maleimide (NMM). [11] Complete site selectivity is possible with the addition of the Lewis acid methyldichloroaluminium. With one set of premixing and 2 equivalents of NMM, the central diene group is targeted to the monoadduct 3. With another set and a larger amount of dienophile, the terminal groups react and the reaction proceeds from the monoadduct to the trisadducts 2 and 2b.

Dendralene NMM diels alder.svg

One reaction variation is cyclopropanation to a compound class called ivyanes with a reported synthesis in a Simmons–Smith reaction (diethyl zinc / trifluoroacetic acid) of the first 6 members. [23] These 1,1-oligocyclopropanes are stable (except when exposed to acids) and have a large heat of combustion with [6]ivyane exceeding that of cubane. The oligocyclopropane chains adopt a helical conformation. For [3]dendralene a photochemical cyclisation reaction has been reported [24]

Derivatives

A bicyclic [4]dendralene compound has been reported. [25]

Related Research Articles

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<span class="mw-page-title-main">Diels–Alder reaction</span> Chemical reaction

In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted mechanism. More specifically, it is classified as a thermally-allowed [4+2] cycloaddition with Woodward–Hoffmann symbol [π4s + π2s]. It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in the synthesis of natural products and new materials. The underlying concept has also been applied to π-systems involving heteroatoms, such as carbonyls and imines, which furnish the corresponding heterocycles; this variant is known as the hetero-Diels–Alder reaction. The reaction has also been generalized to other ring sizes, although none of these generalizations have matched the formation of six-membered rings in terms of scope or versatility. Because of the negative values of ΔH° and ΔS° for a typical Diels–Alder reaction, the microscopic reverse of a Diels–Alder reaction becomes favorable at high temperatures, although this is of synthetic importance for only a limited range of Diels-Alder adducts, generally with some special structural features; this reverse reaction is known as the retro-Diels–Alder reaction.

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<span class="mw-page-title-main">Norbornadiene</span> Chemical compound

Norbornadiene is an organic compound and a bicyclic hydrocarbon. Norbornadiene is of interest as a metal-binding ligand, whose complexes are useful for homogeneous catalysis. It has been intensively studied owing to its high reactivity and distinctive structural property of being a diene that cannot isomerize. Norbornadiene is also a useful dienophile in Diels-Alder reactions.

[n]Radialenes are alicyclic organic compounds containing n cross-conjugated exocyclic double bonds. The double bonds are commonly alkene groups but those with a carbonyl (C=O) group are also called radialenes. For some members the unsubstituted parent radialenes are elusive but many substituted derivatives are known.

<span class="mw-page-title-main">Danishefsky's diene</span> Chemical compound

Danishefsky's diene is an organosilicon compound and a diene with the formal name trans-1-methoxy-3-trimethylsilyloxy-buta-1,3-diene named after Samuel J. Danishefsky. Because the diene is very electron-rich it is a very reactive reagent in Diels-Alder reactions. This diene reacts rapidly with electrophilic alkenes, such as maleic anhydride. The methoxy group promotes highly regioselective additions. The diene is known to react with amines, aldehydes, alkenes and alkynes. Reactions with imines and nitro-olefins have been reported.

<span class="mw-page-title-main">Sulfolene</span> Chemical compound

Sulfolene, or butadiene sulfone is a cyclic organic chemical with a sulfone functional group. It is a white, odorless, crystalline, indefinitely storable solid, which dissolves in water and many organic solvents. The compound is used as a source of butadiene.

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Tetraphenylcyclopentadienone is an organic compound with the formula (C6H5)4C4CO. It is a dark purple to black crystalline solid that is soluble in organic solvents. It is an easily made building block for many organic and organometallic compounds.

In organic chemistry, an intramolecular Diels-Alder cycloaddition is a Diels–Alder reaction in which the diene and a dienophile are both part of the same molecule. The reaction leads to the formation of the same cyclohexene-like structure as usual for a Diels–Alder reaction, but as part of a more complex fused or bridged cyclic ring system. This reaction gives rise to various natural derivatives of decalin.

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The imine Diels–Alder reaction involves the transformation of all-carbon dienes and imine dienophiles into tetrahydropyridines.

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<span class="mw-page-title-main">Thiobenzophenone</span> Chemical compound

Thiobenzophenone is an organosulfur compound with the formula (C6H5)2CS. It is the prototypical thioketone. Unlike other thioketones that tend to dimerize to form rings and polymers, thiobenzophenone is quite stable, although it photoxidizes in air to form benzophenone and sulfur. Thiobenzophenone is deep blue and dissolves readily in many organic solvents.

<span class="mw-page-title-main">Xylylene</span>

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<span class="mw-page-title-main">1,3-Diphenylisobenzofuran</span> Chemical compound

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References

  1. ↑ Henning Hopf, Classics in Hydrocarbon Chemistry, Wiley VCH, 2000.
  2. ↑ Hopf, H.; Sherburn, M. S. (2012). "Dendralenes Branch Out: Cross-Conjugated Oligoenes Allow the Rapid Generation of Molecular Complexity". Angewandte Chemie International Edition in English. 51 (10): 2298–2338. doi:10.1002/anie.201102987. PMID   22337341.
  3. ↑ Preparation and Synthetic Value of π-Bond-Rich Branched Hydrocarbons Michael S. Sherburn Accounts of Chemical Research 2015 48 (7), 1961-1970 doi:10.1021/acs.accounts.5b00242
  4. ↑ Bailey, William J.; Economy, James (1955). "Pyrolysis of Esters. III. Synthesis of 2-Vinylbutadiene". J. Am. Chem. Soc. 77 (5): 1133–1136. doi:10.1021/ja01610a014.
  5. ↑ Blomquist, A. T.; Verdol, Joseph A. (1955). "2-Vinyl-1,3-butadiene". J. Am. Chem. Soc. 77 (1): 81–83. doi:10.1021/ja01606a025.
  6. ↑ Bailey, William J.; Economy, James; Hermes, Mathew E. (1962). "Polymers. IV. Polymeric Diels-Alder Reactions". J. Org. Chem. 27 (9): 3295–3299. doi:10.1021/jo01056a074.
  7. ↑ Mieko Arisawa, Takumichi Sugihara and Masahiko Yamaguchi Synthesis of cross-conjugated trienes by dimerization of allenes with palladium-phenol catalystChem. Commun. 1998; 2615-2616 doi:10.1039/A807527A
  8. ↑ Rekha Singh and Sunil K. Ghosh Synthesis of substituted [3]dendralenes and their unique cycloaddition reactionsChem. Commun. 2011; Advance Article doi:10.1039/C1CC14211A
  9. ↑ Bradford, Tanya A.; Payne, Alan D.; Willis, Anthony C.; Paddon-Row, Michael N.; Sherburn, Michael S. (2007). "Cross-Coupling for Cross-Conjugation:? Practical Synthesis and Diels?Alder Reactions of [3]Dendralenes". Organic Letters. 9 (23): 4861–4864. doi:10.1021/ol7021998. PMID   17929828.
  10. ↑ Kassem Beydoun, Hui-Jun Zhang, Basker Sundararaju, Bernard Demerseman, Mathieu Achard, Zhenfeng Xi and Christian Bruneau Efficient ruthenium-catalyzed synthesis of [3]dendralenes from 1,3-dienic allylic carbonatesChem. Commun. 2009; 6580-6582 doi:10.1039/B913595B
  11. 1 2 3 Payne, Alan D.; Willis, Anthony C.; Sherburn, Michael S. (2005). "Practical Synthesis and Diels−Alder Chemistry of [4]Dendralene". Journal of the American Chemical Society. 127 (35): 12188–12189. doi:10.1021/ja053772+. ISSN   0002-7863. PMID   16131173.
  12. ↑ Molecular Structure of 3,4-Dimethylenehexa-1,5-diene ([4]Dendralene), C8H10, in the Gas Phase As Determined by Electron Diffraction and ab Initio Calculations Paul T. Brain,Bruce A. Smart,Heather E. Robertson,Martin J. Davis,†, David W. H. Rankin,*, William J. Henry, and Ian Gosney The Journal of Organic Chemistry 1997 62 (9), 2767-2773 doi:10.1021/jo962091h
  13. ↑ Practical Synthesis of the Dendralene Family Reveals Alternation in Behavior Alan D. Payne, Gomotsang Bojase, Michael N. Paddon-Row, and Michael S. Sherburn Angew. Chem. Int. Ed. 2009, 48, doi:10.1002/anie.200901733
  14. ↑ Discovery and Computational Rationalization of Diminishing Alternation in [n]Dendralenes Mehmet F. Saglam, Thomas Fallon, Michael N. Paddon-Row, and Michael S. Sherburn Journal of the American Chemical Society 2016 138 (3), 1022-1032 doi:10.1021/jacs.5b11889
  15. ↑ Brummond, Kay M.; You, Lingfeng (2005). "Consecutive Rh(I)-catalyzed Alder-ene/Diels–Alder/Diels–Alder reaction sequence affording rapid entry to polycyclic compounds". Tetrahedron. 61 (26): 6180–6185. doi:10.1016/j.tet.2005.03.141.
  16. ↑ Hopf, H.; Yildizhan, Ş. (2011). "Highly Functionalized, Angularly Anellated Aromatic Compounds from Dendralenes". European Journal of Organic Chemistry. 2011 (11): 2029–2034. doi:10.1002/ejoc.201001536.
  17. ↑ A novel and facile stereocontrolled synthetic method for polyhydro-quinolines and pyridopyridazines via a diene-transmissive Diels–Alder reaction involving inverse electron-demand hetero Diels–Alder cycloaddition of cross-conjugated azatrienes Tetrahedron, Volume 64, Issue 41, 6 October 2008, Pages 9705-9716 Satoru Kobayashi, Tomoki Furuya, Takashi Otani and Takao Saito doi:10.1016/j.tet.2008.07.102
  18. ↑ Synthesis of a Potent Antimalarial Amphilectene Sergey V. Pronin and Ryan A. Shenvi Journal of the American Chemical Society 2012 134 (48), 19604-19606 doi:10.1021/ja310129b
  19. ↑ Green, N. J.; Lawrence, A. L.; Bojase, G.; Willis, A. C.; Paddon-Row, M. N.; Sherburn, M. S. (2013). "Domino Cycloaddition Organocascades of Dendralenes". Angew. Chem. Int. Ed. 52 (32): 8333–8336. doi:10.1002/anie.201302185. PMID   23804245.
  20. ↑ Practical Synthesis and Reactivity of [3]Dendralene Tanya A. Bradford, Alan D. Payne, Anthony C. Willis, Michael N. Paddon-Row, and Michael S. Sherburn The Journal of Organic Chemistry 2010 75 (2), 491-494 doi:10.1021/jo9024557
  21. ↑ Multicomponent Diene-Transmissive Diels–Alder Sequences Featuring Aminodendralenes S. M. Tan, A. C. Willis, M. N. Paddon-Row, M. S. Sherburn, Angew. Chem. Int. Ed. 2016, 55, 3081. doi:10.1002/anie.201510925
  22. ↑ Synthesis and Diels–Alder Reactivity of Substituted [4]Dendralenes Mehmet F. Saglam, Ali R. Alborzi, Alan D. Payne, Anthony C. Willis, Michael N. Paddon-Row, and Michael S. Sherburn The Journal of Organic Chemistry 2016 81 (4), 1461-1475 doi:10.1021/acs.joc.5b02583
  23. ↑ Bojase, Gomotsang; Nguyen, Thanh V.; Payne, Alan D.; Willis, Anthony C.; Sherburn, Michael S. (2011). "Synthesis and properties of the ivyanes: the parent 1,1-oligocyclopropanes" (PDF). Chem. Sci. 2 (2): 229–232. doi:10.1039/C0SC00500B. hdl: 1885/58011 .
  24. ↑ Tetrahedron Letters Volume 35, Issue 29, 18 July 1994, Pages 5251–5252 A novel photochemical reaction of [3]dendralene derivatives Keiji Okada, Katsuji Maehara, Masaji Oda doi:10.1016/S0040-4039(00)77076-6
  25. ↑ Transformation of azulenes to bicyclic [4]dendralene and heptafulvene derivatives via photochemical cycloaddition of dialkylsilylene Tomoyuki Kosai, Shintaro Ishida ,Takeaki Iwamoto Chem. Commun., 2015,51, 10707-10709 doi:10.1039/C5CC03424H
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