Synthesis of natural products and related compounds using enyne metathesis

Since the molybdenum and ruthenium car- bene complexes 1a and 1b were discovered by Schrock and Grubbs in 1990 and 1992, synthetic or- ganic chemistry has progressed with the use of these complexes as the catalyst for olefin metathesis. It was found that the ruthenium carbene complex was also effective for enyne metathesis, which occurs between an alkene and an alkyne. Intramolecular enyne meta- thesis gives various cyclic compounds having a 1,3- diene moiety and cross-metathesis of an alkene with an alkyne is a useful method for the synthesis of a compound having a diene moiety. Furthermore, dien- yne metathesis, ROM of cycloalkenynes or tandem reactions of enyne metathesis have been developed. Using these various enyne metatheses, complicated natural products have been synthesized via novel routes. The syntheses of natural products and related compounds using enyne metathesis are described.

[1]  S. Woo,et al.  Stereoselective synthesis of (-)-amphidinolide E. , 2008, Chemistry, an Asian journal.

[2]  L. Paquette,et al.  Studies directed toward the total synthesis of lancifodilactone G: an expeditious route to the ABC subunit. , 2008, Organic letters.

[3]  M. Mori*.  Ene‐Yne Metathesis , 2008 .

[4]  K. Kaliappan,et al.  Angucyclinone antibiotics: total syntheses of YM-181741, (+)-ochromycinone, (+)-rubiginone B2, (-)-tetrangomycin, and MM-47755. , 2007, The Journal of organic chemistry.

[5]  N. Camp,et al.  Stereocontrolled synthesis of (-)-galanthamine. , 2007, Organic letters.

[6]  F. Boyer,et al.  Synthesis of allocolchicines using sequential ring-closing enyne metathesis-Diels-Alder reactions. , 2007, Organic letters.

[7]  Yoichi Kita,et al.  Further studies on enantioselective synthesis of (+)-anatoxin-a using enyne metathesis: unexpected inversion of chirality via a skeletal rearrangement of 9-azabicyclo[4.2.1]nonene derivative , 2006 .

[8]  G. Domínguez,et al.  Enyne and dienyne metathesis reactions in β-carbolines , 2005 .

[9]  S. Martin,et al.  Application of a domino intramolecular enyne metathesis/cross metathesis reaction to the total synthesis of (+)-8-epi-xanthatin. , 2005, Organic letters.

[10]  O. Bedel,et al.  Diastereoselective Access to the Spirotetronate Subunit of the Quartromicins , 2005 .

[11]  K. Nicolaou,et al.  Metathesis reactions in total synthesis. , 2005, Angewandte Chemie.

[12]  J. Morken,et al.  Asymmetric synthesis of (-)-dihydroxanthatin by the stereoselective Oshima-Utimoto reaction. , 2005, Organic letters.

[13]  B. Straub,et al.  Mechanism of enyne metathesis catalyzed by Grubbs ruthenium-carbene complexes: a DFT study. , 2005, Journal of the American Chemical Society.

[14]  S. Blechert,et al.  Synthesis of cis-fused carbo-bicycles by domino enyne cross-metathesis/intramolecular Diels-Alder Reaction. , 2005, Organic letters.

[15]  M. Mori,et al.  Synthesis of isoquinoline derivatives using ROM-RCM of cyclobutene-yne. , 2005, The Journal of organic chemistry.

[16]  M. Mori,et al.  Synthetic study of (+)-anthramycin using ring-closing enyne metathesis and cross-metathesis , 2004 .

[17]  M. Mori,et al.  ROM-RCM of cycloalkene-yne , 2004 .

[18]  S. Martin,et al.  Enantioselective synthesis of (+)-anatoxin-a via enyne metathesis , 2004 .

[19]  H. Mizutani,et al.  First total synthesis of (+)-viroallosecurinine , 2004 .

[20]  D. S. Reddy,et al.  Efficient and general approach to eremophilanes using siloxyalkyne-alkene metathesis. , 2004, The Journal of organic chemistry.

[21]  Yoichi Kita,et al.  Synthesis of (+)-anatoxin-a using enyne metathesis , 2004 .

[22]  F. Boyer,et al.  Formal synthesis of (+/-)-guanacastepene A: a tandem ring-closing metathesis approach. , 2004, Organic letters.

[23]  M. Rogers-Evans,et al.  A concise asymmetric route to the bridged bicyclic tropane alkaloid ferruginine using enyne ring-closing metathesis. , 2004, Organic letters.

[24]  S. Martin,et al.  Application of intramolecular enyne metathesis to the synthesis of aza[4.2.1]bicyclics: enantiospecific total synthesis of (+)-anatoxin-a. , 2004, Organic letters.

[25]  S. Diver,et al.  Enyne metathesis (enyne bond reorganization). , 2004, Chemical reviews.

[26]  H. Mizutani,et al.  First diastereoselective chiral synthesis of (-)-securinine. , 2004, Organic letters.

[27]  T. Esumi,et al.  Total synthesis of (±)-erythravine based on ring closing dienyne metathesis , 2003 .

[28]  S. Diver,et al.  Cycloheptadiene ring synthesis by tandem intermolecular enyne metathesis. , 2003, Organic letters.

[29]  M. Mori,et al.  Novel synthesis of heterocycles having a functionalized carbon center via nickel-mediated carboxylation: total synthesis of erythrocarine. , 2003, Organic letters.

[30]  L. Grimaud,et al.  Selective domino ring-closing metathesis-cross-metathesis reactions between enynes and electron-deficient alkenes. , 2003, Organic letters.

[31]  S. Blechert,et al.  Recent developments in olefin cross-metathesis. , 2003, Angewandte Chemie.

[32]  S. Halder,et al.  Synthesis of highly functionalized phenylalanine derivatives via cross-enyne metathesis reactions , 2002 .

[33]  M. Mori,et al.  Ruthenium-catalyzed ROM-RCM of cycloalkene-yne. , 2002, Organic letters.

[34]  R. Grubbs,et al.  Formal Vinyl CH Activation and Allylic Oxidation by Olefin Metathesis , 2002 .

[35]  H. Inoue,et al.  Skeletal reorganization of enynes to 1-vinylcycloalkenes catalyzed by GaCl(3). , 2002, Journal of the American Chemical Society.

[36]  S. Blechert,et al.  A Mechanism Switch in Enyne Metathesis Reactions Involving Rearrangement: Influence of Heteroatoms in the Propargylic Position , 2002 .

[37]  S. Blechert,et al.  A new highly efficient ruthenium metathesis catalyst. , 2002, Angewandte Chemie.

[38]  M. Mori,et al.  An improved 1,3-diene synthesis from alkyne and ethylene using cross-enyne metathesis , 2002 .

[39]  C. A. Morales,et al.  Biomimetic synthesis of (-)-longithorone A. , 2002, Journal of the American Chemical Society.

[40]  M. Mori,et al.  Syntheses of anolignans A and B using ruthenium-catalyzed cross-enyne metathesis. , 2002, The Journal of organic chemistry.

[41]  S. Diver,et al.  Ethylene metathesis of sulfur-containing alkynes , 2002 .

[42]  D. S. Reddy,et al.  Siloxyalkyne-Alkene Metathesis: Rapid Access to Highly Functionalized Enones. , 2001, Angewandte Chemie.

[43]  R. Grubbs,et al.  Olefin metathesis involving ruthenium enoic carbene complexes. , 2001, Journal of the American Chemical Society.

[44]  S. Blechert,et al.  Domino metathesis of alkynyl substituted cycloolefins , 2001 .

[45]  M. Mori,et al.  Synthesis of Medium-Sized Ring Compounds Using Enyne Metathesis , 2001 .

[46]  J. Granja,et al.  Access to [6.4.0]carbocyclic systems by tandem metathesis of dienynes. A step toward the synthesis of a PreD3-D3 transition state analogue. , 2001, Organic letters.

[47]  M. Mori,et al.  Ruthenium-catalyzed ring-opening and ring-closing enyne metathesis. , 2001, Organic letters.

[48]  M. Savignac,et al.  Synthetic approach to tricyclic β-lactams using metathesis and Diels–Alder reactions , 2001 .

[49]  A. Fürstner.  Olefin Metathesis and Beyond , 2000 .

[50]  A. Hoveyda,et al.  Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts , 2000 .

[51]  S. Diver,et al.  Expanded scope in ethylene-alkyne cross-metathesis: coordinating heteroatom functionality at the propargylic position. , 2000, Organic letters.

[52]  G. Doherty,et al.  An Asymmetric Synthesis of the Tricyclic Core and a Formal Total Synthesis of Roseophilin via an Enyne Metathesis , 2000 .

[53]  R. Grubbs,et al.  Synthesis of Functionalized Olefins by Cross and Ring-Closing Metatheses , 2000 .

[54]  A. Fürstner,et al.  Ring-Closing Alkyne Metathesis: Application to the Stereoselective Total Synthesis of Prostaglandin E2-1,15-Lactone , 2000 .

[55]  Smulik,et al.  Terminal Alkyne-Ethylene Cross-Metathesis: Reaction of 1-Substituted Propargyl Esters at Elevated Ethylene Pressure. , 2000, The Journal of organic chemistry.

[56]  Sato,et al.  Synthesis of eight-membered ring compounds using enyne metathesis , 2000, Organic letters.

[57]  S. Nolan,et al.  Influence of Sterically Demanding Carbene Ligation on Catalytic Behavior and Thermal Stability of Ruthenium Olefin Metathesis Catalysts , 1999 .

[58]  Kohl,et al.  Highly Active Ruthenium Catalysts for Olefin Metathesis: The Synergy of N-Heterocyclic Carbenes and Coordinatively Labile Ligands. , 1999, Angewandte Chemie.

[59]  R. Grubbs,et al.  Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligands. , 1999, Organic letters.

[60]  T. Vos,et al.  An enyne metathesis/(4 + 2)-dimerization route to (+/-)-differolide. , 1999, Organic letters.

[61]  R. Grubbs,et al.  Increased ring closing metathesis activity of ruthenium-based olefin metathesis catalysts coordinated with imidazolin-2-ylidene ligands , 1999 .

[62]  Jinkun Huang,et al.  Olefin Metathesis-Active Ruthenium Complexes Bearing a Nucleophilic Carbene Ligand , 1999 .

[63]  S. Schürer,et al.  A versatile synthesis of substituted tetrahydropyridines , 1999 .

[64]  J. P. Harrity,et al.  A Recyclable Ru-Based Metathesis Catalyst , 1999 .

[65]  Andrew J. P. White,et al.  Rapid Entry into Mono-, Bi-, and Tricyclic β-Lactam Arrays via Alkene Metathesis , 1998 .

[66]  S. Murai,et al.  Construction of Novel Polycyclic Ring Systems by Transition-Metal-Catalyzed Cycloisomerization of Ene−Ene−Ynes. Interception of a Carbenoid Intermediate in Skeletal Reorganization of Enynes , 1998 .

[67]  M. Mori,et al.  Remarkable Effect of Ethylene Gas in the Intramolecular Enyne Metathesis of Terminal Alkynes. , 1998, The Journal of organic chemistry.

[68]  A. Fürstner,et al.  Platinum- and Acid-Catalyzed Enyne Metathesis Reactions: Mechanistic Studies and Applications to the Syntheses of Streptorubin B and Metacycloprodigiosin , 1998 .

[69]  R. Grubbs,et al.  Ruthenium-Catalyzed Polycyclization Reactions , 1998 .

[70]  S. Blechert,et al.  A Crossed Yne–Ene Metathesis Showing Atom Economy† , 1997 .

[71]  M. Mori,et al.  NOVEL 1,3-DIENE SYNTHESIS FROM ALKYNE AND ETHYLENE BY RUTHENIUM-CATALYZED ENYNE METATHESIS , 1997 .

[72]  K. Undheim,et al.  Ruthenium-catalyzed enyne metathesis in stereoselective preparation of cyclic 1-amino-1-carboxylic acids , 1997 .

[73]  M. Mori,et al.  Total Synthesis of (−)-Stemoamide Using Ruthenium-Catalyzed Enyne Metathesis Reaction , 1996 .

[74]  S. Murai,et al.  PtCl2-Catalyzed Conversion of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes. Anomalous Bond Connection in Skeletal Reorganization of Enynes , 1996 .

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

[76]  M. Mori,et al.  Ruthenium Catalyzed Enyne Metathesis , 1994 .

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

[78]  M. Mori,et al.  Chromium-Catalyzed Intramolecular Enyne Metathesis , 1994 .

[79]  S. Murai,et al.  Highly Selective Skeletal Reorganization of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes Catalyzed by [RuCl2(CO)3]2 , 1994 .

[80]  B. Trost,et al.  A Cycloaddition Approach to Cyclopentenes via Metalladienes as 4.pi. Partners , 1994 .

[81]  B. Trost,et al.  An Approach to Botrydianes: On the Steric Demands of a Metal Catalyzed Enyne Metathesis , 1994 .

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

[83]  B. Trost,et al.  On the mechanism of the TCPCHFB-catalyzed metathesis of 1,6-enyne : evidence for alkylidenepalladium intermediates , 1993 .

[84]  B. Trost,et al.  A Pd-Catalyzed (2 + 2) Cycloaddition. Mechanism of a Pd-Catalyzed Enyne Metathesis. , 1993 .

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

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

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

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

[89]  T. J. Katz,et al.  Reactions of enynes with adsorbed metal-carbenes , 1991 .

[90]  B. Trost,et al.  Mechanistic dichotomies in Pd catalyzed enyne metathesis of cyclic olefins , 1991 .

[91]  B. Trost,et al.  Intramolecular enyne metathesis reaction. Route to bridged bicycles with bridgehead olefins , 1991 .

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

[93]  J. Stille,et al.  A total synthesis of anthramycin. Application of palladium-catalyzed coupling reactions for the attachment of the acrylic side chain , 1989 .

[94]  M. Chiang,et al.  A metal pentadienyl prepared by reacting a metal carbyne with an enyne , 1989 .

[95]  B. Trost,et al.  An unusual mechanism of a palladium-catalyzed intramolecular carbametalation. A novel palladium-catalyzed rearrangement , 1988 .

[96]  K. Oshima,et al.  One-pot synthesis of tetrahydrofuran derivatives from allylic alcohols and vinyl ethers by means of palladium(II) acetate , 1987 .

[97]  T. Sivavec,et al.  Metal-catalyzed rearrangement of alkene-alkynes and the stereochemistry of metallacyclobutene ring opening , 1985 .

[98]  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 .

[99]  R. Grubbs,et al.  The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story. , 2001, Accounts of chemical research.

[100]  M. Mori,et al.  New Synthesis of Piperidine Derivatives via the Chromacyclobutane , 1993 .

[101]  M. Mori,et al.  New synthesis of pyrrolidine derivatives via the chromacyclobutanes generated from enynes and Fischer carbene complexes , 1992 .