Recent advances in olefin metathesis and its application in organic synthesis

Abstract Recent advances in olefin metathesis, focusing on the areas of ring-closing olefin metathesis (RCM) and cross metathesis, are reviewed. Among numerous complexes which show catalytic activities in olefin metathesis, recently developed well-defined [Mo] and [Ru] catalyst systems have proven to be very efficient and tolerant of many functional groups. Examples of RCM are organized into the areas of medium or macrocyclizations, peptide chemistry, tandem ring-opening/ring-closing reactions, and RCM mediated rearrangements. Variation of substrates such as in polymer bound forms has been discussed. Applications of acyclic metathesis and ring-opening cross metathesis are also included.

[1]  J. K. Thomas,et al.  Living Ring-Opening Metathesis Polymerization of 2,3-Difunctionalized- Norbornadienes by Mo(CH-t-Bu)(N-2,6-C(6)H(3)-i-Pr(2)(O-t-Bu)(2) , 1990 .

[2]  Richard E. Taylor,et al.  Towards the synthesis of epothilone A: Enantioselective preparation of the thiazole sidechain and macrocyclic ring closure , 1997 .

[3]  Par Jean‐Louis Hérisson,et al.  Catalyse de transformation des oléfines par les complexes du tungstène. II. Télomérisation des oléfines cycliques en présence d'oléfines acycliques , 1971 .

[4]  S. Nguyen,et al.  Syntheses and activities of new single-component, ruthenium-based olefin metathesis catalysts , 1993 .

[5]  R. Grubbs,et al.  A simple method to polyhydroxylated olefinic molecules using ring-closing olefin metathesis , 1997 .

[6]  K. Nicolaou,et al.  An Olefin Metathesis Based Strategy for the Construction of the JKL, OPQ, and UVW Ring Systems of Maitotoxin , 1996 .

[7]  John A. Tallarico,et al.  Selective Ring-Opening Cross-Metathesis. Short Syntheses of Multifidene and Viridiene , 1995 .

[8]  S. Schreiber,et al.  Single-Step Synthesis of Cell-Permeable Protein Dimerizers That Activate Signal Transduction and Gene Expression , 1997 .

[9]  K. Undheim,et al.  Synthesis of conformationally restricted serine derivatives through ruthenium(II)-catalyzed ring closing metathesis , 1997 .

[10]  R. Linderman,et al.  Conformational Bias by a Removable Substituent. Synthesis of Eight-Membered Cyclic Ethers via Ring-Closing Metathesis , 1997 .

[11]  A. Hoveyda,et al.  Stereoselective Heteroatom-Assisted Allylic Alkylation of Cyclic Ethers with Grignard Reagents. A Convenient Route to Enantiomerically Pure Carbocycles , 1997 .

[12]  Michele L. Randall,et al.  Regio- and Stereoselective Ring-Opening Cross-Metathesis. Rapid Entry into Functionalized Bicyclo[6.3.0] Ring Systems , 1997 .

[13]  S. Nguyen,et al.  Reactions of Ruthenium Carbenes of the Type (PPh3)2(X)2Ru:CH-CH:CPh2 (X = Cl and CF3COO) with Strained Acyclic Olefins and Functionalized Olefins , 1995 .

[14]  D. Goldberg,et al.  Preparation of allylsilanes via cross-metathesis , 1996 .

[15]  R. Grubbs,et al.  Synthesis of Water-Soluble, Aliphatic Phosphines and Their Application to Well-Defined Ruthenium Olefin Metathesis Catalysts , 1996 .

[16]  Joseph W. Ziller,et al.  A Series of Well‐Defined Metathesis Catalysts–Synthesis of [RuCl2(CHR′)(PR3)2] and Its Reactions , 1995 .

[17]  J. Tallarico,et al.  RING-OPENING METATHESIS. A RUTHENIUM CATALYST CAUGHT IN THE ACT , 1997 .

[18]  SonBinh T. Nguyen,et al.  Well-defined ruthenium olefin metathesis catalysts: Mechanism and activity , 1997 .

[19]  R. Grubbs,et al.  The application of catalytic ring-closing olefin metathesis to the synthesis of unsaturated oxygen heterocycles , 1992 .

[20]  J. P. Harrity,et al.  RU-CATALYZED REARRANGEMENT OF STYRENYL ETHERS. ENANTIOSELECTIVE SYNTHESIS OF CHROMENES THROUGH ZR- AND RU-CATALYZED PROCESSES , 1997 .

[21]  B. W. King,et al.  An Efficient Asymmetric Approach to Carbocyclic Nucleosides: Asymmetric Synthesis of 1592U89, a Potent Inhibitor of HIV Reverse Transcriptase. , 1996, The Journal of organic chemistry.

[22]  Scott J. Miller,et al.  Catalytic Ring-Closing Metathesis of Dienes: Application to the Synthesis of Eight-Membered Rings , 1995 .

[23]  A. Hoveyda,et al.  Cascade Catalysis in Synthesis. An Enantioselective Route to Sch 38516 (and Fluvirucin B1) Aglycon Macrolactam , 1995 .

[24]  W. Crowe,et al.  Highly selective cross-metathesis of terminal olefins , 1993 .

[25]  R. Grubbs,et al.  Quantitative Ring-Closing Metathesis of Polyolefins , 1996 .

[26]  Robert H. Grubbs,et al.  High‐Yield Synthesis of [2] Catenanes by Intramolecular Ring‐Closing Metathesis , 1997 .

[27]  H. Overkleeft,et al.  A formal synthesis of castanospermine using an olefin metathesis cyclisation reaction as a key step , 1996 .

[28]  R. Grubbs,et al.  Tandem Ring Opening−Ring Closing Metathesis of Cyclic Olefins , 1996 .

[29]  D. Goldberg,et al.  Acrylonitrile Cross-Metathesis: Coaxing Olefin Metathesis Reactivity from a Reluctant Substrate , 1995 .

[30]  J. S. Clark,et al.  Synthesis of brevetoxin sub-units by sequential ring-closing metathesis and hydroboration , 1997 .

[31]  P. Fuchs,et al.  APPLICATION OF THE GRUBBS RING-CLOSING METATHESIS FOR THE CONSTRUCTION OF A MACROCYCLIC ANSA-BRIDGE. SYNTHESIS OF THE TRICYCLIC CORE OF ROSEOPHILIN , 1997 .

[32]  M. Ghadiri,et al.  SUPRAMOLECULAR DESIGN BY COVALENT CAPTURE. DESIGN OF A PEPTIDE CYLINDER VIA HYDROGEN-BOND-PROMOTED INTERMOLECULAR OLEFIN METATHESIS , 1995 .

[33]  A. Limberg,et al.  Total Synthesis of (−)‐Epothilone A , 1997 .

[34]  R. Grubbs,et al.  Living Ring-Opening Metathesis Polymerization in Aqueous Media Catalyzed by Well-Defined Ruthenium Carbene Complexes , 1996 .

[35]  S. Armstrong,et al.  Synthesis of sulphur-containing heterocycles by ring closing diene metathesis , 1996 .

[36]  A. Fürstner,et al.  Conformationally Unbiased Macrocyclization Reactions by Ring Closing Metathesis. , 1996, The Journal of organic chemistry.

[37]  W. A. Nugent,et al.  Practical catalyst for cyclic metathesis. Synthesis of functional and/or enantiopure cycloalkenes. , 1995 .

[38]  K. Nicolaou,et al.  Total Synthesis of Epothilone A: The Olefin Metathesis Approach , 1997 .

[39]  G. Bazan,et al.  Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins , 1990 .

[40]  T. Chou,et al.  REMOTE EFFECTS IN MACROLIDE FORMATION THROUGH RING-FORMING OLEFIN METATHESIS : AN APPLICATION TO THE SYNTHESIS OF FULLY ACTIVE EPOTHILONE CONGENERS , 1997 .

[41]  K. Undheim,et al.  Ruthenium(II) in ring closing metathesis for the stereoselective preparation of cyclic 1-amino-1-carboxylic acids , 1997 .

[42]  S. Nguyen,et al.  The syntheses and activities of polystyrene-supported olefin metathesis catalysts based on Cl2(PR3)2Ru = CH−CH = CPh2 , 1995 .

[43]  J. Tsuji,et al.  Application of olefin metathesis to organic synthesis. Syntheses of civetone and macrolides , 1980 .

[44]  A. B. Dyatkin Ring-closing olefin metathesis for the synthesis of 1,8-diazabicyclo[4.3.0]non-3-ene-7,9-diones , 1997 .

[45]  S. Nguyen,et al.  Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media , 1992 .

[46]  R. Grubbs,et al.  Synthesis of Cycloalkenes via Alkylidene‐Mediated Olefin Metathesis and Carbonyl Olefination. , 1993 .

[47]  T. Lee,et al.  Catalytic ring-closing olefin metathesis of sulfur-containing species: Heteroatom and other effects , 1997 .

[48]  R. Grubbs,et al.  Asymmetric Ring-Closing Metathesis: Kinetic Resolution Catalyzed by a Chiral Molybdenum Alkylidene Complex , 1996 .

[49]  R. Grubbs,et al.  SYNTHESIS OF NEW CHIRAL LIGANDS AND THEIR GROUP VI METAL ALKYLIDENE COMPLEXES , 1996 .

[50]  J. Dewan,et al.  Preparation and reactions of tantalum alkylidene complexes containing bulky phenoxide or thiolate ligands. Controlling ring-opening metathesis polymerization activity and mechanism through choice of anionic ligand , 1988 .

[51]  J. Ziller,et al.  Alkylidene transfer from phosphoranes to tungsten(IV) imido complexes , 1993 .

[52]  Robert H. Grubbs,et al.  Ring-Closing Metathesis and Related Processes in Organic Synthesis , 1995 .

[53]  R. Grubbs,et al.  The synthesis of nitrogen heterocycles via catalytic ring-closing metathesis of dienes , 1992 .

[54]  M. Leconte,et al.  Metathesis of sulfur-containing olefins with a metallacyclic aryloxo(chloro)neopentylidenetungsten complex , 1993 .

[55]  J. S. Clark,et al.  Enantioselective synthesis of medium-ring sub-units of brevetoxin A by ring-closing metathesis , 1997 .

[56]  A. Hoveyda,et al.  Catalytic and Enantioselective Route to Medium-Ring Heterocycles. Asymmetric Zirconium-Catalyzed Ethylmagnesation of Seven- and Eight-Membered Rings , 1996 .

[57]  A. Fürstner,et al.  Macrocycle Formation by Ring-Closing-Metathesis. 2. An Efficient Synthesis of Enantiomerically Pure (R)-(+)-Lasiodiplodin , 1996 .

[58]  M. Leconte,et al.  A Cyclometalated Aryloxy(chloro)neopentylidenetungsten Complex: A Highly Active and Stereoselective Catalyst for the Metathesis of cis‐ and trans‐2‐Pentene, Norbornene, 1‐Methyl‐norbornene, and Ethyl Oleate , 1992 .

[59]  Chuan Yi Tang,et al.  A 2.|E|-Bit Distributed Algorithm for the Directed Euler Trail Problem , 1993, Inf. Process. Lett..

[60]  S. Nguyen,et al.  Catalytic ring-closing metathesis of functionalized dienes by a ruthenium carbene complex , 1993 .

[61]  W. M. Davis,et al.  Preparation of Biscarboxylato Imido Alkylidene Complexes of Molybdenum and Cyclopolymerization of Diethyldipropargylmalonate To Give a Polyene Containing only Six-Membered Rings , 1996 .

[62]  K. Nicolaou,et al.  Synthesis of epothilones A and B in solid and solution phase , 1997, Nature.

[63]  A. Bell Aryloxide derivatives of tungsten oxytetrachloride as ring-opening metathesis polymerization catalysts , 1992 .

[64]  G. Bazan,et al.  Living ring-opening metathesis polymerization of 2,3-difunctionalized 7-oxanorbornenes and 7-oxanorbornadienes by Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(O-tert-Bu)2 and Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(OCMe2CF3)2 , 1991 .

[65]  W. M. Davis,et al.  Metathetical reactions of rhenium(VII) alkylidene-alkylidyne complexes of the type Re(CR')(CHR')[OCMe(CF3)2]2 (R' = CMe3 or CMe2Ph) with terminal and internal olefins , 1993 .

[66]  A. Hoveyda,et al.  Enantioselective Total Synthesis of Antifungal Agent Sch 38516 , 1996 .

[67]  W. A. Nugent,et al.  Highly Efficient and Enantioselective Synthesis of Carbocyclic Nucleoside Analogs Using Selective Early Transition Metal Catalysis. , 1996, The Journal of organic chemistry.

[68]  Scott J. Miller,et al.  Synthesis of Conformationally Restricted Amino Acids and Peptides Employing Olefin Metathesis , 1995 .

[69]  K. Nicolaou,et al.  Olefin Metathesis in Cyclic Ether Formation. Direct Conversion of Olefinic Esters to Cyclic Enol Ethers with Tebbe-Type Reagents , 1996 .

[70]  R. Grubbs,et al.  Template-Directed Ring-Closing Metathesis: Synthesis and Polymerization of Unsaturated Crown Ether Analogs† , 1997 .

[71]  G. M. Visser,et al.  Solid phase ring-closing metathesis: Cyclization/cleavage approach towards a seven membered cycloolefin , 1996 .

[72]  Scott J. Miller,et al.  Application of Ring-Closing Metathesis to the Synthesis of Rigidified Amino Acids and Peptides , 1996 .

[73]  H. Schoemaker,et al.  Ruthenium-catalyzed ring closing olefin metathesis of non-natural α-amino acids , 1997 .

[74]  K. J. Ivin,et al.  First direct observation of the simultaneous presence and of the interconversion of chain-propagating metal-carbene and metallacyclobutane complexes in a catalytic olefin metathesis reaction: the ring-opening polymerization of norbornene , 1987 .

[75]  J. Ziller,et al.  Synthesis and Applications of RuCl2(CHR‘)(PR3)2: The Influence of the Alkylidene Moiety on Metathesis Activity , 1996 .

[76]  S. Blechert,et al.  Selective Ring‐Opening Olefin Metathesis of Functionalized Monosubstituted Olefins , 1997 .

[77]  S. Blechert,et al.  Synthesis of Highly Substituted Cyclopentane and Tetrahydrofuran Derivatives by Crossed Olefin Metathesis , 1996 .

[78]  R. Grubbs,et al.  Catalytic Ring Closing Metathesis of Dienynes: Construction of Fused Bicyclic [n.m.0] Rings , 1994 .

[79]  K. J. Ivin,et al.  Olefin metathesis and metathesis polymerization , 1997 .