本論文以醛基形式插烯化交叉共軛予體進行聯繼插烯化Michael / HWE反應時，意外發現醛基形式交叉共軛二烯醇陰離子可作為新穎之二烯，與親二烯物進行陰離子Diels-Alder 環加成反應，得到符合endo形式Diels-Alder環加成之產物。這一新穎二烯所建構位向專一之Diels-Alder產物具有稠化雙環烯酮次結構，在合成化學中可提供各種衍生化發展。

This thesis details the discovery of an unexpected access to endo-form cycloaddition products during our efforts on development of the anionic annulation. The key process is an anionic Diels-Alder cycloaddition between an aldehyde type cross-conjugated dienolate and electron deficient dienophile. This novel reaction enabled the production of fused bicyclic enone substructure in a one-step operation, which allowed us to provide various regio- and stereo-specific derivatives in synthetic organic chemistry.

摘要 I
Abstract II
謝誌 III
縮寫對照表 V
目錄 VI
第一章 緒論 1
1.1 建立環狀化合物 1
1.2 Robinson[4+2]增環反應 4
1.3 Hauser[4+2]增環反應 6
1.4 Deslongchamps[4+2]環化反應 9
1.5 本論文研究之實驗設計 13
第二章 實驗結果與討論 15
2.1 醛基形式插烯化交叉共軛予體1之製備 15
2.2 聯繼插烯化Michael /HWE反應之實驗結果 21
2.3 生成副產物芳香氰化合物5之可能機制 23
2.4 醛基予體反應條件篩選及探討 26
2.5 擴展不同親二烯物之範疇及討論 37
2.6 研究不同Dienolate結構上對反應之影響 44
第三章 結論 49
第四章 實驗步驟與光譜資料 50
4.1一般化學實驗方法 50
4.1.1醛基形式交叉共軛化合物1之製備 52
4.1.2化合物1進行陰離子Diels-Alder環加成反應之擴展 55
4.1.3 不同二烯醇陰離子進行陰離子Diels-Alder環加成反應之擴展 73
第五章 參考文獻 80
附 錄 82
X-射線單晶繞射 83
核磁共振 96

(1) McGrath, N. A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ. 2010, 87, 1348.
(2) Rapson, W. S.; Robinson, R. J. Chem. Soc. 1935, 1285.
(3) Eisenhuth, W.; Renfroe, H. B.; Schmid, H. Helv. Chim. Acta 1965, 48, 375.
(4) Little, R. D.; Dawson, J. R. Tetrahedron Lett. 1980, 21, 2609.
(5) Mal, D. In Anionic Annulations in Organic Synthesis; Mal, D., Ed.; Elsevier: 2019, p 1.
(6) Marinetti, A.; Jullien, H.; Voituriez, A. Chem. Soc. Rev. 2012, 41, 4884.
(7) C. A. Grob, W. B. Helv. chim. Acta 1955, 38.
(8) Dugger, R. W.; Ragan, J. A.; Ripin, D. H. B. Org. Process Res. Dev. 2005, 9, 253.
(9) Gallier, F.; Martel, A.; Dujardin, G. Angew. Chem. Int. Ed. 2017, 56, 12424.
(10) Takaki, K.; Okada, M.; Yamada, M.; Negoro, K. J. Org. Chem. 1982, 47, 1200.
(11) Bui, T.; Barbas, C. F. Tetrahedron Lett. 2000, 41, 6951.
(12) Li, P.; Payette, J. N.; Yamamoto, H. J. Am. Chem. Soc. 2007, 129, 9534.
(13) Hauser, F. M.; Rhee, R. P. J. Org. Chem. 1978, 43, 178.
(14) Kraus, G. A.; Sugimoto, H. Tetrahedron Lett. 1978, 19, 2263.
(15) Mal, D. In Anionic Annulations in Organic Synthesis; Mal, D., Ed.; Elsevier: 2019, p 31.
(16) Ingold, C. K. Obituary Notices of Fellows of the Royal Society 1941, 3, 531.
(17) Sun, C.; Wang, Q.; Brubaker, J. D.; Wright, P. M.; Lerner, C. D.; Noson, K.; Charest, M.; Siegel, D. R.; Wang, Y.-M.; Myers, A. G. J. Am. Chem. Soc. 2008, 130, 17913.
(18) Huang, J.-K.; Yang Lauderdale, T.-L.; Lin, C.-C.; Shia, K.-S. J. Org. Chem. 2018, 83, 6508.
(19) Wang, S.; Kraus, G. A. J. Org. Chem. 2018, 83, 15549.
(20) Chenard, B. L.; Anderson, D. K.; Swenton, J. S. J. Chem. Soc., Chem. Commun. 1980, 932.
(21) Hauser, F. M.; Prasanna, S. J. Am. Chem. Soc. 1981, 103, 6378.
(22) Evans, G. E.; Leeper, F. J.; Murphy, J. A.; Staunton, J. J. Chem. Soc., Chem. Commun. 1979, 205.
(23) Mal, D. In Anionic Annulations in Organic Synthesis; Mal, D., Ed.; Elsevier: 2019, p 373.
(24) Lavallée, J.-F.; Deslongchamps, P. Tetrahedron Lett. 1988, 29, 5117.
(25) Ravindar, K.; Caron, P.-Y.; Deslongchamps, P. Org. Lett. 2013, 15, 6270.
(26) Huang, J.-K.; Shia, K.-S. Angew. Chem. Int. Ed. 2020, 59, 6540.
(27) Jr., W. S. W. In Org. React. 2005, p 73.
(28) Brenton, A. G.; Godfrey, A. R. J. Am. Soc. Mass. Spectrom. 2010, 21, 1821.
(29) Elisabeth, C.; Anizon, F.; Aboab, B.; Prudhomme, M. Synthesis 2008, 2008, 2569.
(30) Feltenberger, J. B.; Hsung, R. P. Org. Lett. 2011, 13, 3114.
(31) Crump, D. R. J. Chem. Soc., Perkin Trans. 1 1979, 646.
(32) Hent, A.; Andraos, J. In Strategies and Solutions to Advanced Organic Reaction Mechanisms; Hent, A., Andraos, J., Eds.; Academic Press: 2019, p 337.
(33) Fernández, I.; Bickelhaupt, F. M. J. Comput. Chem. 2014, 35, 371.
(34) Duhamel, L.; Guillemont, J.; Poirier, J.-M.; Chabardes, P. Tetrahedron Lett. 1991, 32, 4499.
(35) Regueira, M. A.; Samanta, S.; Malloy, P. J.; Ordóñez-Morán, P.; Resende, D.; Sussman, F.; Muñoz, A.; Mouriño, A.; Feldman, D.; Torneiro, M. J. Med. Chem. 2011, 54, 3950.
(36) Johnson, F. Chem. Rev. 1968, 68, 375.
(37) Malhotra, S. K.; Johnson, F. J. Am. Chem. Soc. 1965, 87, 5493.
(38) Rafiński, Z.; Krzeminski, M. Catalysts 2019, 9, 117.