上海有机所合成讲义第13讲.ppt

Hetero Diels-Alder Reaction Stereochemistry Tetrahedron 1971, 27, 3119; Heterocycles 1979, 12, 949; J. Am. Chem. Soc. 1973, 95, 5273. Hetero Diels-Alder Reaction Stereochemistry Tetrahedron Lett. 1981, 4607. Miscellaneous Dienophiles C-N triple bond C-S double bond N-O double bond Miscellaneous Dienophiles N-S double bond S-S, S-O, Se-O double bond P-S double bond N-N triplele bond Hetero Diels-Alder Reaction-total synthesis Hetero Diels-Alder Reaction-total synthesis Hetero Diels-Alder Reaction-total synthesis Hetero Diels-Alder Reaction-total synthesis Hetero Diels-Alder Reaction Suggested references Hetero Diels-Alder Methodology in Organic Synthesis, Boger, D.L. and Weinreb, S.N., Academic Press, 1987 Mechanistic Aspects of Diels-Alder Reactions: A Critical Survey, Sauer, Angew. Chem. Int. Ed., 1980, 19, 779-807 DA Reactions Part II: The Reaction Mechanism, Sauer, Angew. Chem. Int. Ed., 1967, 6, 16-33 DA Reactions Part I: New Preparative Aspects, Sauer, Angew. Chem. Int. Ed., 1966, 5, 211-230 Synthetic Aspects of D-A Cycloadditions with Heterodienophiles, Weinreb, Tetrahedron, 1982, 38, 3087-3128 [2+2] cycloaddition [2+2] cycloaddition [2+2] cycloaddition-Reaction types F2C=CX2(X=F, Cl) especially F2C=CF2 form cyclobutanes with many alkenes. ([2+2] preferred with conjugated diene) Allenes and ketenes react with activated olefins and alkyne to form cyclobutanes. ([2+2] preferred with conjugated diene for ketenes) Benzynes undergoes [2+2] with certain olefins Enamides form four-membered rings with Michael-type olefins and ketenes Sch?fer, Angew. Chem. 1967, 79, 54. Dauben, Tet. 1961, 15, 197. Sch?fer, Angew. Chem. 1967, 79, 54. Dauben, Tet. 1961, 15, 197. Summary of Ketene Cycloadditions State Key Lab of Organometallic Chem, SIOC, China Lewis acid tuned regioselectivity A model Lewis acid tuned regioselectivity explanation Similar results provided by Stoodley, Chem. Comm. 1982, 929 Lewis acid tuned regioselectivity a second model Similar results provided by