Synthesis and trapping of spiro [bicyclo[4.2.0]octa-2,3-diene-7,2'-[1,3]dioxolane]

Year 2023, Volume: 12 Issue: 3, 131 - 138, 31.12.2023

Mustafa Ceylan , Esra Koç

https://doi.org/10.54187/jnrs.1355406

Abstract

Spiro[bicyclo[3.2.0]hept-2-ene-6,2'-[1,3]dioxolane] was synthesized by the reaction of bicyclo[3.2.0]hept-2-en-6-one with ethylene glycol in yield of 92%. Addition of dichlorocarbene to Spiro[bicyclo[3.2.0]hept-2-ene-6,2'-[1,3]dioxolane] gave the 3',3'-Dichlorospiro[1,3-dioxolane-2,7'-tricyclo[4.2.0.02,4]octane] in 50 % yields. Finally, the 3',3'-Dichlorospiro[1,3-dioxolane-2,7'-tricyclo[4.2.0.02,4]octane] was submitted to Doering-Moore-Skatebol reaction for the synthesis of allene precursors. The reaction of the 3',3'-Dichlorospiro[1,3-dioxolane-2,7'-tricyclo[4.2.0.02,4] octane] with methyl lithium (MeLi) in the presence of 1,3-diphenylisobenzofuran (DBI) as a trapping reagent under a nitrogen atmosphere at ca. 0 ℃ was started and continued at room temperature for four hours, resulting in the formation of four cyclo adduct isomers of spiro[bicyclo[4.2.0]octa-2,3-diene-7,2'-[1,3]dioxolane].

Keywords

Allene, 1,2-Cyclohexadiene, Carbene, Doering-Moore-Skatebol reaction

References

• M. Balcı, Y. Taşkesenliğil, Advances in strained and interesting organic molecules, Vol. 8 of Recent Developments in Strained Cyclic Allenes, JAI Press, Stamford, Connecticut, 2000, pp. 43–81.
• R. P. Johnson, Strained cyclic cumulenes, Chemical Reviews 89 (5) (1989) 1111–1124.
• M. Nendel, L. M. Tolbert, L. A. Herring, Md. N. Islam, K. N. Houk, Strained allenes as dienophiles in the Diels−Alder reaction:  an experimental and computational study, Journal of Organic Chemistry 64 (3) (1999) 976–983.
• M. Christl, M. Braun, Freisetzung und Abfangreaktionen von 1-Oxa-2,3-cyclohexadien, Chemische Berichte 122 (10) (1989) 1939–1946.
• Y. Sütbeyaz, M. Ceylan, H. Seçen, A novel synthesis of 1,2-cyclohexadiene and 1,2- cycloheptadiene by the elimination of $\beta$-Halosilane, Journal of Chemical Research 8 (1993) 2189–2196.
• W. J. Ball, S. R. Landor, Allenes. Part III. The synthesis of cyclic allenes, Journal of Chemical Society (1962) 2298–2304.
• G. Wittig, P. Fritze, On the intermediate occurrence of 1,2-cyclohexadiene, Angewandte Chemie International Edition English 5 (9) (1966) 846–846.
• W. R. Moore, W. R. Moser, Reaction of 6,6-dibromobicyclo[3.1.0]hexane with methyllithium. Evidence for the generation of 1,2-cyclohexadiene and 2,2'-dicyclohexenylene, Journal of American Chemistry Society 92 (18) (1970) 5469–5474.
• M. Balcı, W. M. Jones, Chirality as a probe for the structure of 1,2-cycloheptadiene and 1,2-cyclohexadiene, Journal of American Chemistry Society 102 (25) (1980) 7607–7608.
• M. Ceylan, H. Seçen, Y. Sütbeyaz, Attempted synthesis of cyclopenta-1,2-diene and Wurtz-like condensation products in the reaction of 2,3-dibromocycloalkenes with zinc, Journal of Chemical Research, Synopses (3) (1997) 70–71.
• M. Ceylan, Y. Budak, Attempted synthesis of 1-pheny-1, 2-cyclohexadiene and Wurtz-like condensation products in the reaction of 1-(2,3-dibromocyclohex-1-en-1-yl) benzene with zinc, Journal of Chemical Research 2001 (9) (2001) 368–369.
• M. Ceylan, Y. Budak, Synthesis of 1-phenyl-1, 2-cyclohexadiene and 1-(2-bromocyclohex-2-en-1-yl)benzene and Wurtz-like condensation products in the reaction of 1-(2,3-dibromocyclohex-1-en-1-yl) benzene with zinc, Journal of Chemical Research 2002 (9) (2002) 416–419.
• M. Ceylan, Y. Budak, M. Ulukaya, M. B. Gürdere, E. Fındık, Synthesis and isolation of 1-cyclohex-1,2-dien-1-ylbenzenefrom 1-(2-Iodocyclohex-1-en-1-yl)benzene and 1-(2-Iodocyclohex-2-en-1-yl)benzene, Turkish Journal of Chemistry 31 (6) (2007) 647–657.
• M. Ceylan, Y. Budak, M. B. Gürdere, Attempted synthesis of 1-cyclohepta-1,2-dien-1-ylbenzene and Wurtz-like condensation products in the reaction of 1-(2,3-dibromocyclohept-1-en-1-yl)benzene with zinc, Turkish Journal of Chemistry 30 (5) (2006) 635–642.
• M. Ceylan, S. Yalçın, H. Seçen, Y. Sütbeyaz, M. Balcı, Evidence for the formation of a new five-membered ring cyclic allene: Generation of 1-cyclopenta-1,2-dien-1-ylbenzene, Journal of Chemical Research 2003 (1) (2003) 21–23.
• B. Wang, M.-G. Constantin, S. Singh, Y. Zhou, R. L. Davis, F. G. West, Generation and trapping of electron-deficient 1,2-cyclohexadienes. Unexpected hetero-Diels–Alder reactivity, Organic and Biomolecular Chemistry 19 (2) (2021) 399–405.
• V. A. Lofstrand, K. C. McIntosh, Y. A. Almehmadi, F. G. West, Strain-activated Diels–Alder trapping of 1,2-cyclohexadienes: intramolecular capture by pendent furans, Organic Letters 21 (16) (2019) 6231–6234.
• K. Inoue, R. Nakura, K. Okano, A. Mori, One-pot synthesis of silylated enol triflates from silyl enol ethers for cyclohexynes and 1,2-cyclohexadienes, European Journal of Organic Chemistry 2018 (25) (2018) 3343–3347.
• Y. Hioki, A. Mori, K. Okano, Steric effects on deprotonative generation of cyclohexynes and 1,2-cyclohexadienes from cyclohexenyl triflates by magnesium amides, Tetrahedron 76 (22) (2020) Article Number 131103 10 pages.
• M. S. McVeigh, N. K. Garg, Interception of 1,2-cyclohexadiene with TEMPO radical, Tetrahedron Letters 87 (2021) Article Number 153539 4 pages.