Rh2(OAc)4-Catalyzed Reactions of α,β-Conjugated Enon Compounds with 2-Diazo-5,5-Dimethyl-1,3-Cyclohexandione

Yıl 2024, Cilt: 14 Sayı: 1, 249 - 261, 15.03.2024

Füsun Şeyma Güngör , Ayşe Özdemir

https://doi.org/10.31466/kfbd.1393378

Öz

Reactions of α,β-conjugated enone compounds, and 2-diazo-5,5-dimethyl-1,3-hexanedione were carried out under the dirhodium tetraacetate (Rh2(OAc)4) catalyst. The structures of the obtained products were characterized by FT-IR, GC-MS, 1H NMR, and 13C NMR methods. 6,6-Dimethyl-3,5,6,7-tetrahydro-4H-spiro[benzofuran-2,2'-bicyclo[2.2.1]heptane]-3',4-dione was obtained from the reaction of 3-methylidene-bicyclo[2.2.1]heptan-2-one, the first α,β-conjugated enone compound used in the study, as a single product. The second α,β-conjugated enone compound, 1-morpholinoprop-2-en-1-one, did not react with Rh-carbene, and only the carbene dimer was obtained from this reaction.

Anahtar Kelimeler

Diazodicarbonyl, Conjuge Enone, Dihydrofuran, Rh2(OAc)4

Proje Numarası

İTÜ-Bap proje ID-kod 9039-1819

α,β-Konjuge Enon Bileşiklerinin 2-Diazo-5,5-Dimetil-1,3-Sikloheksandion ile Rh2(OAc)4-Katalizli Tepkimeleri

Öz

α,β-Konjuge enon bileşikleri ile 2-diazo-5,5-dimetil-1,3-heksandionun dirodyum tetraasetat (Rh2(OAc)4) katalizörlüğünde tepkimeleri gerçekleştirilmiştir. Elde edilen ürünlerin yapıları FT-IR, GC-MS ve 1H NMR ve 13C NMR yöntemleri ile karakterize edilmiştir. Çalışmada kullanılan ilk α,β-konjuge enon bileşiği olan 3-metiliden-bisiklo[2.2.1]heptan-2-onun tepkimesinden 6,6-dimetil-3,5,6,7-tetrahidro-4H-spiro[benzofuran-2,2’-bisiklo[2.2.1]heptan]-3’,4-dion bileşiği tek ürün olarak elde edilmiştir. İkinci α,β-konjuge enon bileşiği olan 1-morfolinoprop-2-en-1-on Rh-karbeni ile tepkime vermemiş olup bu tepkimeden sadece karben dimeri elde edilmiştir.

Anahtar Kelimeler

Diazodikarbonil, Konjuge Enon, Dihidrofuran, Rh2(OAc)4

Etik Beyan

Yapılan çalışmada araştırma ve yayın etiğine uyulmuştur.

Destekleyen Kurum

İ.T.Ü. Bilimsel Araştırmalar Proje Birimi

Proje Numarası

İTÜ-Bap proje ID-kod 9039-1819

Teşekkür

Bu çalışma İ.T.Ü. Bilimsel Araştırmalar Proje Birimi tarafından (Proje no: İTÜ-Bap proje ID-kod 9039-1819) desteklenmiştir.

Kaynakça

• Anac, O., and Daut, A. (1997). Reactions of α,β-enones with diazo compounds. Part 2: Synthesis of dihydrofuran derivatives. Liebigs Annalen / Recuil, 6, 1249-1254. doi: https://doi.org/10.1002/jlac.199719970630
• Anac, O., Daut-Ozdemir, A., and Sezer, O. (2003). Reactions of α,β-enones with diazo compounds. Part 3: On the natüre of the 1,5-ring closure of α,β-enone ylides. Helvetica Chimica Acta, 86(2), 290-298. doi: https://doi.org/10.1002/hlca.200390030
• Anac, O., Gungor, F. S., Kahveci, C., and Cansever, M. S. (2004). Reactions of α,β-enones with diazo compounds. Part 4: Reaction pathways from (Z)- and (E)- α,β-enones with dimethyl diazo malonate. Helvetica Chimica Acta, 87(2), 408-415. doi: https://doi.org/10.1002/hlca.200490039
• Anac, O., and Gungor, F. S. (2010). Electrocyclization reactions of vinyl, styryl, and butadienyl conjugated carbonyl/azomethine ylides. Tetrahedron, 66, 5931-5953. doi: https://doi.org/10.1016/j.tet.2010.05.058
• Celik, M. A., Yurtsever, M., Tuzun, N. S., Gungor, F. S., Sezer, O., and Anac, O. (2007). Metal-catalyzed cyclization reactions of carbonyl ylides: Synthesis and DFT study of mechanisms. Organometallics, 26(12), 2978-2985. doi: https://doi.org/10.1021/om0609970
• Chapyshev, S. V., Nakano, H., and Ibata, T. (1996). Formal C-H insertion of diketocarbene generated by rhodium(II)-catalyzed decomposition of diazodimedone into a benzene molecule. Russian Chemical Bulletin, 45, 471-473. doi: https://doi.org/10.1007/BF01434000
• Cornell, R., Scavo, F., Helquist, P., and Akermark, B. (1986). Functionalized oxazoles from rhodium(II)-catalyzed reaction of dimethyl diazomalonate with nitriles. Tetrahedron Letters, 27(46), 5559-5562. doi: https://doi.org/10.1016/S0040-4039(00)85265-X
• Davies, H. M. L., and Romines, K. R. (1988). Direct synthesis of furan by 3 + 2 cycloaddition between rhodium(II) acetate stabilized carbenoids and acetylenes. Tetrahedron, 44(11), 3343-3348. doi: https://doi.org/10.1016/S0040-4020(01)85968-8
• Daut-Ozdemir, A., Anaç, O., and Somer, M. (2002). Crystal Structure of 3R(S)-1'S(R)-2,2-Dimethoxycarbonyl-3-(2',6',6'-trimethyl-2'-cyclo¬hexen-1'-yl)2,3-dihydrofuran, C18H26O5. Zeitschrift für Kristallographie- New Crystal Structures, 217, 607-608. doi: https://doi.org/10.1524/ncrs.2002.217.jg.607
• Dean, F. M. (1982). Advances in Heterocyclic Chemistry. In A. R. Katritzky (Ed.), (Vol 30, pp. 167-238). New York NY: Academic Press.
• Dean, F. M., and Sargent, M. V. (1984). Comprehensive Heterocyclic Chemistry. In C. W. Bird and G. W. H. Cheeseman (Eds.) (Vol 4, pp. 531-598). NY: Pergamon Press.
• Doyle, M. P., McKervey, T., and Ye, T. (1988). Modern catalytic methods for organic synthesis with diazo compounds. New York: Wiley
• Gungor, F. S., Anac, O., and Sezer, O. (2011). Synthesis of naphthalenone, dihydroquinoline, and dihydrofuran derivatives. Helvetica Chimica Acta, 94(6), 1115-1129. doi: https://doi.org/10.1002/hlca.201000386
• Gungor, F. S., Merey, G., and Anac, O. (2020). Chemoselective carbenoid reactions of furan/thiophene/pyrrole ring containing carbonyl and conjugated carbonyl at their 2-positions. ChemistrySelect, 5, 5337-5340. doi: 10.1002/slct.202000584
• Jaques, R., Pal, R., Parker, N. A., Sear, C. E., Smith, P. W., Ribaucourt, A., and Hodgson, D. M. (2016). Recent applications in natural product synthesis of dihydrofuran and pyran formation by ring-closing alkene metathesis. Organic & Biomolecular Chemistry, 14, 5875-5893. doi: https://doi.org/10.1039/C6OB00593D
• Kilroy, T. G., O’sullivan, T. P., and Guiry, P. J. (2005). Synthesis of dihydrofurans substituted in the 2-position. European Journal of Organic Chemistry, 23, 4929-4949. doi: https://doi.org/10.1002/ejoc.200500489
• Kışkan, F. Ş. (2023). Copper-catalyzed reactions of β-alkoxy/phenoxy enones with dimethyl diazomalonate. Turkish Journal of Chemistry, 47(1), 81-87. doi: 10.55730/1300-0527.3519
• Konnur, S. B., and Nandibewoor, S. T. (2019). Kinetic investigations of ruthenium(III) catalyzed oxidation of dimedone by diperiodatocuprate(III) in aqueous alkaline media. Russian Journal of Physical Chemistry A, 93(9), 1686-1698. doi: https://doi.org/10.1134/S003602441909022X
• Lee, Y. R., and Suk, J. Y. (1998). Efficient synthesis of β-substituted α-chloro enones by rhodium(II)-catalyzed reactions of cyclic diazodicarbonyl compounds with acid chlorides. Chemical Communications, 2621-2622. doi: https://doi.org/10.1039/A806993J
• Lee, Y. R., Suk, J. Y., and Kim, B. S. (1999). Rhodium(II)-catalyzed reactions of 3-diazo-2,4-chromenediones. First one-step synthesis of pterophyllin 2. Tetrahedron Letters, 36(3), 6603-6607. doi: https://doi.org/10.1016/S0040-4039(99)01317-9
• Lee, Y. R., Suk, J. Y., and Kim, B. S. (1999). Efficient synthesis of oxindoles by thermal and rhodium(II)-catalyzed Wolff rearrangement. Tetrahedron Letters, 40(17), 8219-8221. doi: https://doi.org/10.1016/S0040-4039(99)01714-1
• Lee, Y. R., and Kim, D. H. (2001). Novel method fort he synthesis of β-substituted α-haloenones by rhodium(II)-catalyzed reactions of diazodicarbonyl compounds with benzyl halides. Tetrahedron Letters, 42(37), 6561-6563. doi: https://doi.org/10.1016/S0040-4039(01)01345-4
• Lee, Y. R., and Suk, J. Y. (2002). Efficient synthesis of dihydrofurans and furans by rhodium(II)-catalyzed reactions of cyclic diazodicarbonyl compounds. Tetrahedron, 58(12), 2359-2367. doi: https://doi.org/10.1016/S0040-4020(02)00118-7
• Lee, Y. R., Cho, B. S., and Kwon, H. J. (2003). A convinient and efficient preparation of β-substituted α-haloenones from diazdicarbonyl compounds. Tetrahedron, 59(47), 9333-9347. doi: https://doi.org/10.1016/j.tet.2003.09.087
• Lee, Y. R., Hwang J. C. (2005). Efficient synthesis of five-and seven-membered-ring heterocycles by rhodium(II)-catalyzed [3+2] and [3+4] cycloaddition of diazodicarbonyl compounds with conjugated dienes. European Journal of Organic Chemistry, 1568-1577. doi: https://doi.org/10.1002/ejoc.200400452
• Padwa, A., and Kinder, F. R. (1993). Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans. Journal Of Organic Chemistry, 58(1), 21-28. doi: https://doi.org/10.1021/jo00053a009
• Regitz, M., and Stadler, D. (1965). Reaktionen aktiver methylenverbindungen mit Aziden VIII. Über α,α'-azo-β-dicarbonylverbindungen bzw . deren tautomere. Ein beitrag aliphatischen azokupplung. Justus Liebigs Annalen der Chemie, 687(1), 214-231. doi: https://doi.org/10.1002/jlac.19656870120
• Shevchenko, V. V., Shakhmin, A. A., and Nikolaev, V. A. (2006). Catalytic decomposition of 5-diazo-2,2-dimethyl-1,3-dioxane-4,6-dione and its analogs. Russian Journal of Organic Chemistry, 42, 1741-1744. doi: https://doi.org/10.1134/S1070428006110273
• Shi, G., and Xu, Y. (1989). Ethyl 3-trifluoro-2-diazo-propionate as a potentially useful CF3-containing building block: Preparation and [Rh(OAc)2]2-catalysed reaction with nitriles. Journal of the Chemical Society, Chemical Communications, 607-608. doi: 10.1039/C39890000607
• Slavinskaya, V. A., Karakhanov, R. A., Brezhnev, L. Y., Geiman, I. I., Bulenkova, L. F., and Strautinya, A. K. (1982). Catalytic synthesis of dihydrofurans. Chemistry of Heterocyclic Compounds, 18, 997-1008. doi: https://link.springer.com/article/10.1007/BF00503178
• Spencer, T. A., Villarica, R. M., Storm, D. L., Weaver, T. D., Friary, R. J., Posler, J., Shafer, P. R. (1967). Total synthesis of racemic methyl vinhaticoate. Journal of American Chemical Society, 89(21), 5497-5499. doi: https://doi.org/10.1021/ja00997a060
• Storm, D. L., and Spencer, T. A. (1967). Furan synthesis by 1,4 addition of carboethoxycarbene to α-methoxymethylene ketones. Tetrahedron Letters, 8(20), 1865-1867. doi: https://doi.org/10.1016/S0040-4039(00)90743-3
• Ye, T., and, McKervey, M. A. (1994). Organic synthesis with alpha-diazo carbonyl compounds. Chemical Reviews, 94, 1091-1160. doi: https://doi.org/10.1021/cr00028a010
• Zheng, J.-C., Zhu, C.-Y., Sun, X.-L., Tang, Y., and Dai, L.-X. (2008). Highly diastereoselective and enantioselective formal [4+1] ylide annulation for the synthesis of optically active dihydrofurans. Journal of Organic Chemistry, 73(17), 6909-6912. doi: https://doi.org/10.1021/jo801135j
• Zhou, J.-L., Liang, Y., Deng, C., Zhou, H., Wang, Z., Sun, X.-L., Zheng, J.-C., Yu, Z.-X., and Tang, Y. (2011). Tunable carbonyl ylide reactions: Selective synthesis of dihydrofurans and dihydrobenzoxepines. Angewandte Chemie International Edition, 50(34), 7874-7878. doi: https://doi.org/10.1002/anie.201100551
• Zhou, J.-L., Wang, L.-J., Xu, H., Sun, X.-L., and Tang, Y. (2013). Highly enantioselective synthesis of multifunctionalized dihydrofurans by copper-catalyzed asymmetric [4+1] cycloadditions of α-benzylidene-β-ketoester with diazo compound. ACS Catalysis, 3(4), 685-688. doi: https://doi.org/10.1021/cs400019u