Materials Basel. Published online Mar Miwako Mori.
Author information Article notes Copyright and License information Disclaimer. Abstract Olefin metathesis using ruthenium carbene complexes is a useful method in synthetic organic chemistry. Keywords: enyne metathesis, ring-closing enyne metathesis, dienyne metathesis, cross metathesis, ring-opening metathesis, natural product.
Table of Content Introduction 1. Ring-Closing Enyne Metathesis 2. Ring-Closing Dienyne Metathesis 3. Cross Enyne Metathesis 4. Ring-Opening Enyne Metathesis 5. Skeletal Reorganization Using Transition Metals 6.
Metallotropic Rearrangement Perspective. Introduction Since the discovery of molybdenum and ruthenium carbene complexes by Schrock and Grubbs in [ 1 ] and [ 2 ], synthetic organic chemistry has made rapid progress using metathesis reactions. Open in a separate window. Figure 1. Figure 2. Scheme 1. Scheme 2. Ring-Closing Enyne Metathesis RCM Mori reported the synthesis of heterocycles having a diene moiety using enyne metathesis [ 35 , 36 ].
Scheme 4. Metathesis of enyne having terminal alkyne under ethylene gas. Scheme 5.
Enyne metathesis using second generation ruthenium catalysts. Scheme 6.
Scheme 7. Scheme 8. Scheme 9. Syntheses of Natural Products and Related Compounds Using Ring-Closing Enyne Metathesis RCM The first example of the total synthesis of a natural product using ring-closing enyne metathesis is the synthesis of - -stemoamide [ 57 , 58 ]. Ring-Closing Dienyne Metathesis Grubbs reported an ingenious method for synthesizing bicyclic compounds from dienynes taking advantage of the metathesis reaction Scheme 31 [ 81 , 82 ].
Base-promoted isomerization of propargyl amide followed by RCM. Syntheses of Natural Products and Related Compounds Using Dienyne Metathesis Dienyne metathesis is a useful method for the synthesis of fused bicyclic or polycyclic compounds in one step, and many bond fissions and bond formations occur during the dienyne metathesis. Synthetic study directed toward the total synthesis of ilexlactone.
Formal total synthesis of - -cochleamycin A using dienyne metathesis. Cross Enyne Metathesis A novel synthetic procedure of 1,3-diene from alkyne and ethylene using cross enyne metathesis was developed in by Mori [ 97 , 98 ].
Table 1 Synthesis of Various 1,3-dienes from alkyne and alkene using 1g. One pot synthesis of nitrogen heterocycles using cross metathesis. Synthesis of Natural Products and Related Compounds Using Cross Metathesis Synthesis of natural products using cross metathesis is interesting because 1,3-diene moiety is constructed onto the alkyne carbons at the later step.
Ring-Opening Enyne Metathesis Tandem metathesis of cycloalkene-ynes is a unique reaction because different cyclic compound is formed from the starting cycloalkene via many steps by a one operation. Synthesis of isoquinoline derivatives using ROM of cyclobutene-yne. Skeletal Reorganization Using Transition Metals Trost discovered palladium-catalyzed enyne metathesis during the course of his study on palladium-catalyzed enyne cyclization [ , , , , , , ]. Synthesis of Natural products Using Skeletal Reorganization Skeletal reorganization is a useful tool for the synthesis of complicated natural products.
Formal total synthesis of streptorubin B and metacycloprodigiosin. Metallotropic Rearrangement The bond reorganization processes, defined as metallotropic shift, of various alkynyl carbene complexes with Rh [ ], Mn [ ], Re [ ], Cr [ ], Mo [ ], and W [ ] metals have been already reported. Synthesis of Natural Products Using Metallotropic Rearrangement The metallotropic [1,3] shift of a transient ruthenium carbene complex is involved in the enyne ring-closing metathesis of diyne containing substrates.
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Perspective Since the discovery of stable and isolable catalysts for metathesis by Schrock and Grubbs, a wide range of olefin metatheses have been reported, and olefin metathesis now plays an important role in natural product syntheses. References 1. Schrock R. Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins. Nguyen S.
The application of catalytic ring-closing olefin metathesis to the synthesis of unsaturated oxygen heterocycles. The synthesis of nitrogen heterocycles via catalytic ring-closing metathesis of dienes. Synthesis of cycloalkenes via alkylidene-mediated olefin metathesis and carbonyl olefination. Catalytic ring-closing metathesis of functionalized dienes by a ruthenium carbene complex.
Schwab P. Weskamp T. A novel class of ruthenium catalysts for olefin metathesis. Huang J. Olefin metathesis-active ruthenium complexes bearing a nucleophilic carbene ligand. Influence of sterically demanding carbene ligation on catalytic behavior and thermal stability of ruthenium olefin metathesis catalysts. Scholl M. Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1,3-dimesityl-4,5-dihydroimidazolylidene ligands.
Platinum- and Acid-Catalyzed Enyne Metathesis Reactions
Increased ring closing metathesis activity of ruthenium-based olefin metathesis catalysts coordinated with imidazolinylidene ligands. Tetrahedron Lett. Chaterjee A. Synthesis of functionalized olefins by cross and ring-closing metatheses. Choi T. Olefin metathesis involving ruthenium enoic carbene complexes. Chatterjee A. Formal vinyl CH activation and allylic oxidation by olefin metathesis.
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Enyne metathesis - Wikipedia
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