Cyclopentenone

Cyclopentenone
Names
Preferred IUPAC name
Cyclopent-2-en-1-one
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.012.012 Edit this at Wikidata
UNII
  • InChI=1S/C5H6O/c6-5-3-1-2-4-5/h1,3H,2,4H2 checkY
    Key: BZKFMUIJRXWWQK-UHFFFAOYSA-N checkY
  • C1CC(=O)C=C1
Properties
C5H6O
Molar mass 82.102 g·mol−1
Density 0.98 g·mL−1
Boiling point 150 °C (302 °F; 423 K)
almost insoluble in water
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Harmful
Flash point 42 °C (108 °F; 315 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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2-Cyclopentenone is the organic compound with the chemical formula (CH2)2(CH)2CO. 2-Cyclopentenone contains two functional groups, a ketone and an alkene. It is a colorless liquid. Its isomer, 3-cyclopentenone is less commonly encountered.

The term cyclopentenone may also refer to a structural motif wherein the cyclopentenone moiety is a subunit of a larger molecule. Cyclopentenones are found in a large number of natural products, including jasmone, the aflatoxins, and several prostaglandins.[1]

Synthesis

2-Cyclopentenones can be synthesized in a number of ways. One of the routes involves elimination of α-bromo-cyclopentanone using lithium carbonate[2] and Claisen condensation-decarboxylation-isomerization cascades of unsaturated diesters as shown below.[3]

Industrial synthesis of cyclopentenone
Industrial synthesis of cyclopentenone

The acid-catalyzed dehydration of cyclopentanediols affords cyclopentenone.[4]

As a functional group, the synthesis of 2-cyclopentenones is accomplished in a variety of other ways, including the Nazarov cyclization reaction from divinyl ketones, Saegusa–Ito oxidation from cyclopentanones, ring-closing metathesis from the corresponding dienes, oxidation of the corresponding cyclic allylic alcohols, and the Pauson–Khand reaction from alkenes, alkynes, and carbon monoxide.[5]

Reactions

As an enone, 2-cyclopentenone undergoes the typical reactions of α-β unsaturated ketones, including nucleophilic conjugate addition, the Baylis–Hillman reaction, and the Michael reaction. Cyclopentenone also functions as an excellent dienophile in the Diels–Alder reaction, reacting with a wide variety of dienes. In one example, a Danishefsky-type diene is reacted with a cyclopentenone to yield a fused tricyclic system en route to the synthesis of coriolin.[6]

Cyclopentenone in the synthesis of coriolin
Cyclopentenone in the synthesis of coriolin

Occurrence

It has been isolated from pressure-cooked pork liver by simultaneous steam distillation and continuous solvent extraction.[7][8]

References

  1. ^ Simeonov, Svilen P.; Nunes, João P. M.; Guerra, Krassimira; Kurteva, Vanya B.; Afonso, Carlos A. M. (2016-05-25). "Synthesis of Chiral Cyclopentenones". Chemical Reviews. 116 (10): 5744–5893. doi:10.1021/cr500504w. ISSN 0009-2665. PMID 27101336.
  2. ^ US EP1418166, Daisuke, Fukushima & Norihiko, Hirata, "Process for producing 2-bromocyclopentanone", published 2004-05-12 
  3. ^ US EP1422212, Liang, Shelue; Haunert, Andrea & Huber-Dirr, Sylvia et al., "Process for preparing cyclopentenone", published 2004-11-25 
  4. ^ Charles H. DePuy; K. L. Eilers (1962). "2-Cyclopentenone". Org. Synth. 42: 38. doi:10.15227/orgsyn.042.0038.
  5. ^ Müller, Reto. "Synthesis of cyclopentenones". Organic Chemistry Portal. Retrieved 3 March 2015.
  6. ^ Danishefsky, Samuel; Zamboni, Robert; Kahn, Michael; Etheredge, Sarah Jane (March 1980). "Total synthesis of dl-coriolin". Journal of the American Chemical Society. 102 (6): 2097–2098. doi:10.1021/ja00526a061.
  7. ^ Mussinan, Cynthia J.; Walradt, John P. (May 1974). "Volatile constituents of pressure cooked pork liver". Journal of Agricultural and Food Chemistry. 22 (5): 827–831. doi:10.1021/jf60195a002.
  8. ^ Simeonov, Svilen P.; Nunes, João P. M.; Guerra, Krassimira; Kurteva, Vanya B.; Afonso, Carlos A. M. (2016). "Synthesis of Chiral Cyclopentenones". Chemical Reviews. 116 (10): 5744–5893. doi:10.1021/cr500504w. PMID 27101336.
  9. ^ A. G. Ross, X. Li, S. J. Danishefsky (2012). "Preparation of Cyclobutenone". Organic Syntheses. 89: 491. doi:10.15227/orgsyn.089.0491.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  10. ^ Y. Ito, S. Fujii, M. Nakatuska, F. Kawamoto,T. Saegusa (1979). "One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenones: 2-Cyclohepten-1-One". Organic Syntheses. 59: 113. doi:10.15227/orgsyn.059.0113.{{cite journal}}: CS1 maint: multiple names: authors list (link)