用FeCl3·6H2O催化3-甲基环己酮与丙酮酸乙酯交叉羟醛缩合,制得2-(2-氧代-4-甲基环己叉基)丙酸乙酯和7a-羟基薄荷内酯,皂化后用硼氢化钠还原、酸化制得(±)-薄荷内酯,产率为51％.考察了3-甲基环己酮的烯醇式异构化的位置选择性和粗产物中(±)-薄荷内酯与(±)-异薄荷内酯异构体的比例.
参考文献
| [1] | Gaudin J M.Synthesis and Organoleptic Properties ofp-Menthane Lactones[J].Tetrahedron,2000,56(27):4769-4776. |
| [2] | Serra S,Fuganti C.Enzyme-Mediated Preparation of Enantiomerically Pure p-Mentha-3,9-diols and Their Use for the Synthesis of Natural p-Menthane Lactones and Ethers[J].Helv Chim Acta,2002,85(8):2489-2502. |
| [3] | Ferraz H M C,Jr L S L,Grazini M V A.Syntheses of Mintlactone and Isomintlactone[J].Synthesis,2002,34(15):2155-2164. |
| [4] | Bates R W,Sridhar S J.A Synthesis of (-)-Mintlactone[J].J Org Chem,2008,73(20):8104-8105. |
| [5] | Tsubuki M,Takahashi K,Honda T.Practical Ruthenium-Catalyzed Cyclocarbonylation of Allenyl Alcohols in 2,4,6-Collidine Leading to α,β-Unsaturated Lactones:Concise Stereoselective Synthesis of (+)-Isomintlactone[J].J Org Chem,2009,74 (3):1422-1425. |
| [6] | Gao P,Xu P F,Zhai H B.Expeditious Construction of (+)-Mintlactone via Intramolecular Hetero-Pauson-Khand Reaction[J].J Org Chem,2009,74(6):2592-2593. |
| [7] | Tanabe Y,Mitarai K,Higashi T,et al.Efficient One-step Synthesis of Trialkylsubstituted 2 (5H)-Furanones Utilizing Direct Ti-crossed Aldol Condensation and Its Application to the Straightforward Synthesis of (R)-Mintlactone and (R)-Menthofuran[J].Chem Commun,2002,38(21):2542-2543. |
| [8] | Bolm C,Legros J,Paih J L,et al.Iron-Catalyzed Reactions in Organic Synthesis[J].Chem Rev,2004,104(12):6217-6254. |
| [9] | Liu L X.Recent Uses of Iron Catalysts in Organic Reactions[J].Curr Org Chem,2010,14(11):1099-1126. |
| [10] | Aoyama N,Manabe K,Kobayashi S.Iron(Ⅲ) Chloride as aWater-Compatible Lewis Acid for Diastereoselective Aldol Reactions in Water in the Presence of a Surfactant[J].Chem Lett,2004,33(3):312-313. |
| [11] | Zhang X Y,Fan X S,Niu H Y,et al.A Novel Green Preparation of α,α'-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl3·6H2O in Ionic Liquid[J].Chinese Chem Lett,2003,14(10):1005-1007. |
| [12] | Li H J,Li W J,Li Z P.Iron-catalyzed Cross-aldol Reactions of ortho-Diketones and Methyl Ketones[J].Chem Commun,2009,45 (22):3264-3266. |
| [13] | Crisp G T,Meyer A G.Synthesis of Optically Active α-Methylene γ-Butyrolactones and (+)-Mintlactone[J].Tetrahedron,1995,51(20):5831-5846. |
| [14] | Antony A,Maloney T.The Effect of Solvent and Cation on the Isomer Ratio of the Enolates of 3-Methylcyclohexanone[J].J Org Chem,1972,37 (7):1055-1056. |
| [15] | Frérot E,Bagnoud A,Vuilleumier C.Menthofurolactone:A New p-Menthane Lactone in Mentha piperita L.:Analysis,Synthesis and Olfactory Properties[J].Flavour Fragr J,2002,17(3):218-226. |
| [16] | Fujita T,Watanabe S,Miharu K,et al.A Convenient Preparative Method for Mintlactone and Isomintlactone[J].J Chem Tech Biotechnol,1985,35 (2):57-62. |
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