Bicyclobutane

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Bicyclobutane
Bicyclobutane-2.svg
Names
Preferred IUPAC name
Bicyclo[1.1.0]butane
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
UNII
  • InChI=1S/C4H6/c1-3-2-4(1)3/h3-4H,1-2H2
    Key: LASLVGACQUUOEB-UHFFFAOYSA-N
  • C1C2C1C2
Properties
C4H6
Molar mass 54.092 g·mol−1
Appearancecolorless gas
Boiling point 8.3 ± 0.2 °C
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bicyclo[1.1.0]butane is an organic compound with the formula C4H6. It is a bicyclic molecule consisting of two cis -fused cyclopropane rings, and is a colorless and easily condensed gas. [1] Bicyclobutane is noted for being one of the most strained compounds that is isolatable on a large scale [2]

Contents

Manufacture and properties

Bicyclobutane is highly strained — its strain energy is estimated at 63.9 kcal mol−1. It is a nonplanar molecule, with a dihedral angle between the two cyclopropane rings of 123°. [2]

The first reported bicyclobutane was the ethyl carboxylate derivative, C4H5CO2Et, which was prepared by dehydrohalogenation the corresponding bromocyclobutanecarboxylate ester with sodium hydride. [2] The parent hydrocarbon was prepared from 1-bromo-3-chlorocyclobutane by conversion of the bromocyclobutanecarboxylate ester, [1] followed by intramolecular Wurtz coupling using molten sodium. [3] The intermediate 1-bromo-3-chlorocyclobutane can also be prepared via a modified Hunsdiecker reaction from 3-chlorocyclobutanecarboxylic acid using mercuric oxide and bromine: [4]

Wurtz-reaction Bicyclobutane synthesis.svg

Stereochemical evidence indicates that bicyclobutane undergoes thermolysis to form 1,3-butadiene with an activation energy of 41 kcal mol−1 via a concerted pericyclic mechanism (cycloelimination, [σ2s+σ2a]). [5]

Derivatives

Bicyclo[1.1.0]butanes are explored in medicinal chemistry as covalent reactive groups. [6]

In the simplest case, double cyclopropanation of acetylene with a copper catalyst gives a 1:1 mixture of cyclopropenes and symmetric bicyclobutanes. [7] Other symmetric bicyclobutanes form from functionalization of benzvalene. [8]

A synthetic approach to more substituted bicyclobutane derivatives involves ring closure of a suitably substituted 2-bromo-1-(chloromethyl)cyclopropane with magnesium in THF, [9] or methyllithium in diethyl ether (lithium-halogen exchange). [10]

Substituted bicyclo[1.1.0]butanes can also be prepared from the reaction of iodo-bicyclo[1.1.1]pentanes with amines, thiols, and sulfinate salts: [11]

Bicyclo[1.1.1]pentanes to Bicyclo[1.1.0]butanes SchemeBCBs.svg
Bicyclo[1.1.1]pentanes to Bicyclo[1.1.0]butanes

Biological synthesis

Linolenic acid can be converted into its bicyclobutane derivative using a fusion protein produced by a strain of the cyanobacterium Anabaena sphaerica (strain PCC 7120). [12] The other group reported a directed evolution approach, whereby engineered heme protein was expressed in E. coli and optimized for rate and yield of a substituted bicyclobutane derivative. [13]

See also

References

  1. 1 2 Wiberg, K. B.; Lampman, G. M.; Ciula, R. P.; Connor, D. S.; Schertler, P.; Lavanish, J. (1965). "Bicyclo[1.1.0]butane". Tetrahedron . 21 (10): 2749–2769. doi:10.1016/S0040-4020(01)98361-9.
  2. 1 2 3 Wiberg, K. B. (1968). "Small Ring Bicyclo[n.m.0]alkanes". In Hart, H.; Karabatsos, G. J. (eds.). Advances in Alicyclic Chemistry. Vol. 2. Academic Press. pp. 185–254. ISBN   9781483224213.
  3. ↑ Lampman, Gary M.; Aumiller, James C. (1971). "Bicyclo[1.1.0]butane". Organic Syntheses . 51: 55. doi:10.15227/orgsyn.051.0055 .
  4. ↑ Lampman, Gary M.; Aumiller, James C. (1971). "Mercury(II) oxide-modified Hunsdiecker reaction: 1-Bromo-3-chlorocyclobutane". Organic Syntheses . 51: 106. doi:10.15227/orgsyn.051.0106 .
  5. ↑ Woodward, Robert B.; Hoffmann, Roald (1969). "The Conservation of Orbital Symmetry". Angewandte Chemie International Edition . 8 (11): 781–853. doi:10.1002/anie.196907811.
  6. ↑ Tokunaga, Keisuke; Sato, Mami; Kuwata, Keiko; Miura, Chizuru; Fuchida, Hirokazu; Matsunaga, Naoya; Koyanagi, Satoru; Ohdo, Shigehiro; Shindo, Naoya; Ojida, Akio (2020-10-28). "Bicyclobutane Carboxylic Amide as a Cysteine-Directed Strained Electrophile for Selective Targeting of Proteins" . Journal of the American Chemical Society . 142 (43): 18522–18531. doi:10.1021/jacs.0c07490. ISSN   0002-7863. PMID   33047956.
  7. ↑ Ramazanov, R.; Yaroslavova, A. V.; Dzhemilev, U. M. (2012) [13 May 2011]. "Synthesis of cyclopropane compounds". Russian Chemical Reviews . 81 (8). Translated by Nikitina, P. A. Turpion: 704–705. doi:10.1070/RC2012v081n08ABEH004230.
  8. ↑ Leininger, Hartmut; Christl, Manfred (1980). "Oxidation reactions of benzvalene". Angewandte Chemie. 19 (6) (International (English) ed.). Weinheim: Verlag Chemie: 458–459. doi:10.1002/anie.198004581.
  9. ↑ D'yachenko, A. I.; Abramova, N. M.; Zotova, S. V.; Nesmeyanova, O. A.; Bragin, O. V. (1985). "New synthesis of bicyclo[1.1.0]butane hydrocarbons". Bulletin of the Academy of Sciences of the USSR. 34 (9): 1885–1889. doi:10.1007/BF00953929. S2CID   96988412.
  10. ↑ Weber, Jürgen; Haslinger, Ulrike; Brinker, Udo H. (16 July 1999). "1-Bromobicyclo[1.1.0]butane as an easily obtainable C4-building block". The Journal of Organic Chemistry. 64 (16). American Chemical Society. doi:10.1021/jo980190k.
  11. ↑ Mandler, Michael D.; Mignone, James; Jurica, Elizabeth A.; Palkowitz, Maximilian D.; Aulakh, Darpandeep; Cauley, Anthony N.; Farley, Christopher A.; Zhang, Shasha; Traeger, Sarah C.; Sarjeant, Amy; Paiva, Anthony; Perez, Heidi L.; Ellsworth, Bruce A.; Regueiro-Ren, Alicia (10 November 2023). "Synthesis of Bicyclo[1.1.0]butanes from Iodo-Bicyclo[1.1.1]pentanes" . Organic Letters . 25 (44). American Chemical Society: 7947–7952. doi:10.1021/acs.orglett.3c01417. ISSN   1523-7060. PMID   37284784.
  12. ↑ Schneider, Claus; Niisuke, Katrin; Boeglin, William E.; Voehler, Markus; Stec, Donald F.; Porter, Ned A.; Brash, Alan R. (2007-11-27). "Enzymatic synthesis of a bicyclobutane fatty acid by a hemoprotein lipoxygenase fusion protein from the cyanobacterium Anabaena PCC 7120". Proceedings of the National Academy of Sciences of the United States of America . 104 (48): 18941–18945. Bibcode:2007PNAS..10418941S. doi: 10.1073/pnas.0707148104 . ISSN   1091-6490. PMC   2141887 . PMID   18025466.
  13. ↑ Chen, Kai; Huang, Xiongyi; Kan, S. B. Jennifer; Zhang, Ruijie K.; Arnold, Frances H. (6 April 2018). "Enzymatic construction of highly strained carbocycles". Science. 360 (6384): 71–75. Bibcode:2018Sci...360...71C. doi:10.1126/science.aar4239. ISSN   1095-9203. PMC   6104391 . PMID   29622650.
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