Asymmetric Heck Reaction

The asymmetric Heck reaction is a powerful method for the synthesis of both tertiary and quaternary chiral carbon centers, with an enantiomeric excess often greater than 80%, and in some cases much higher (up to 99% ee). A variety of carbocyclic and heterocyclic systems can be constructed, including spirocyclic systems. The scope of the reaction with respect to the product alkene isomerization is somewhat limited by problems of regioselectivity, however, these problems are surmountable, and a new generation of ligands that dissociate more rapidly from the products, might improve both enantio- and regiocontrol. A variety of chiral compounds prepared by the asymmetric Heck reaction were successfully utilized in the enantioselective syntheses of complex natural products.

[1]  S. Bräse Synthesis of Bis(enolnonaflates) and their 4-exo-trig-Cyclizations by Intramolecular Heck Reactions , 1999 .

[2]  P. Guiry,et al.  2,2-Dimethyl-2,3-dihydrofuran, a new substrate for intermolecular asymmetric Heck reactions , 1999 .

[3]  M. Shibasaki,et al.  The synthesis of a new palladacycle catalyst. Development of a high performance catalyst for Heck reactions , 1999 .

[4]  P. Meier,et al.  SYNTHESIS OF NEW CHIRAL BIDENTATE (PHOSPHINOPHENYL)BENZOXAZINE P, N-LIGANDS , 1999 .

[5]  M. Hayashi,et al.  Enantioselective Heck reactions using chiral P,N-ligands , 1999 .

[6]  M. Shibasaki,et al.  SYNTHETIC STUDIES ON (+)-WORTMANNIN. AN ASYMMETRIC CONSTRUCTION OF AN ALLYLIC QUATERNARY CARBON CENTER BY A HECK REACTION , 1999 .

[7]  M. Shibasaki,et al.  Silver salt effects on an asymmetric heck reaction. Catalytic asymmetric total synthesis of (+)-xestoquinone , 1998 .

[8]  T. Kida,et al.  Diphenylphosphinooxazoline ligands with a chiral binaphthyl backbone for Pd-catalyzed allylic alkylation , 1998 .

[9]  Y. Uozumi,et al.  Synthesis and application of novel chiral phosphino-oxazoline ligands with 1,1′-binaphthyl skeleton , 1998 .

[10]  P. Diaz,et al.  NEW SYNTHETIC RETINOIDS OBTAINED BY PALLADIUM-CATALYZED TANDEM CYCLISATION-HYDRIDE CAPTURE PROCESS , 1998 .

[11]  M. Shibasaki,et al.  Synthesis and evaluation of a new chiral ligand: 2-diphenylarsino-2′-diphenylphosphino-1,1′-binaphthyl (BINAPAs) , 1998 .

[12]  E. Corey,et al.  The Catalytic Enantioselective Construction of Molecules with Quaternary Carbon Stereocenters. , 1998, Angewandte Chemie.

[13]  F. Laporte,et al.  The Use of a Ten‐Membered Tetraphosphole Macrocycle to Increase the Lifetime of a Palladium Catalyst , 1997 .

[14]  M. Hayashi,et al.  Enantioselective Heck Reactions Catalyzed by Chiral Phosphinooxazoline-Palladium Complexes , 1997 .

[15]  M. Reetz,et al.  Systhesis and Catalytic Activity of Dendritic Diphosphane Metal Complexes , 1997 .

[16]  M. Beller,et al.  Palladacycles: Efficient New Catalysts for the Heck Vinylation of Aryl Halides , 1997 .

[17]  Christopher D. J. Boden,et al.  Synthesis and evaluation of a new chiral arsine ligand; 2,2′-bis(diphenylarsino)-1,1′-binaphthyl (BINAs) , 1997 .

[18]  L. Overman,et al.  Asymmetric Heck Reactions via Neutral Intermediates: Enhanced Enantioselectivity with Halide Additives Gives Mechanistic Insights , 1997 .

[19]  A. Hallberg,et al.  Intramolecular Enantioselective Palladium-Catalyzed Heck Arylation of Cyclic Enamides. , 1997, The Journal of organic chemistry.

[20]  R. Middleton,et al.  The intramolecular Heck reaction , 1997 .

[21]  A. Hallberg,et al.  Microwave-Promoted Palladium-Catalyzed Coupling Reactions , 1996 .

[22]  L. Tietze,et al.  Enantioselective Total Synthesis and Absolute Configuration of the Natural Norsesquiterpene 7‐Demethyl‐2‐methoxycalamenene by a Silane‐Terminated Intramolecular Heck Reaction , 1996 .

[23]  S. Maddaford,et al.  TOTAL SYNTHESIS OF (+)-XESTOQUINONE USING AN ASYMMETRIC PALLADIUM-CATALYZED POLYENE CYCLIZATION , 1996 .

[24]  C. Zechel,et al.  Combinatorial Synthesis of Small Organic Molecules , 1996 .

[25]  A. Hallberg,et al.  Controlled Double-Bond Migration in Palladium-Catalyzed Intramolecular Arylation of Enamidines. , 1996, The Journal of organic chemistry.

[26]  W. Yun,et al.  Heck reaction on solid support: synthesis of indole analogs , 1996 .

[27]  S. Gilbertson,et al.  The combinatorial synthesis of chiral phosphine ligands , 1996 .

[28]  M. Shibasaki,et al.  Asymmetric Heck Reaction−Carbanion Capture Process. Catalytic Asymmetric Total Synthesis of (−)-Δ9(12)-Capnellene , 1996 .

[29]  M. Sodeoka,et al.  Catalytic Asymmetric Synthesis of Halenaquinone and Halenaquinol. , 1996 .

[30]  A. Hallberg,et al.  Regiochemical Control and Suppression of Double Bond Isomerization in the Heck Arylation of 1-(Methoxycarbonyl)-2,5-dihydropyrrole. , 1996, The Journal of organic chemistry.

[31]  L. Tietze Domino Reactions in Organic Synthesis. , 1996, Chemical reviews.

[32]  K. K. Hii,et al.  Characterization of Reactive Intermediates in Palladium‐Catalyzed Arylation of Methyl Acrylate (Heck Reaction) , 1996 .

[33]  S. Sartori,et al.  DRAMATIC INCREASE OF TURNOVER NUMBERS IN PALLADIUM-CATALYZED COUPLING REACTIONS USING HIGH-PRESSURE CONDITIONS , 1996 .

[34]  P. Meier,et al.  CHIRAL PHOSPHANYLDIHYDROOXAZOLES IN ASYMMETRIC CATALYSIS : ENANTIOSELECTIVE HECK REACTIONS , 1996 .

[35]  C. Copéret,et al.  Cyclic Carbopalladation. A Versatile Synthetic Methodology for the Construction of Cyclic Organic Compounds. , 1996, Chemical reviews.

[36]  Jonathan A. Ellman,et al.  Synthesis and Applications of Small Molecule Libraries. , 1996, Chemical reviews.

[37]  S. Taudien,et al.  Towards new ferrocenyl ligands for asymmetric catalysis , 1996 .

[38]  K. Wärnmark,et al.  DESIGN OF CHIRAL LIGANDS FOR ASYMMETRIC CATALYSIS : FROM C2-SYMMETRIC SEMICORRINS AND BISOXAZOLINES TO NON-SYMMETRIC PHOSPHINOOXAZOLINES , 1996 .

[39]  M. Sodeoka,et al.  Catalytic asymmetric synthesis of a versatile intermediate for diterpene syntheses. Regioselective olefin insertion in asymmetric Heck reactions , 1995 .

[40]  M. Beller,et al.  Palladacycles as Efficient Catalysts for Aryl Coupling Reactions , 1995 .

[41]  M. Beller,et al.  Palladacycles as Structurally Defined Catalysts for the Heck Olefination of Chloro- and Bromoarenes†‡ , 1995 .

[42]  P. Wipf Synthetic Studies of Biologically Active Marine Cyclopeptides , 1995 .

[43]  L. Tietze,et al.  Stereo‐ and regioselective intramolecular heck reaction of α‐amino acid derivatives for the synthesis of enantiopure 3,4‐dihydroisoquinolinones , 1995 .

[44]  M. Sodeoka,et al.  REGIOSELECTIVE OLEFIN INSERTION IN ASYMMETRIC HECK REACTION. CATALYTIC ASYMMETRIC SYNTHESIS OF A VERSATILE INTERMEDIATE FOR DITERPENE SYNTHESES , 1995 .

[45]  W. Cabri,et al.  Recent Developments and New Perspectives in the Heck Reaction , 1995 .

[46]  S. Sakuraba,et al.  Synthesis of (β-N-Sulfonylaminoalkyl)phosphines and Their Use in Palladium-Mediated Asymmetric Synthesis , 1995 .

[47]  L. Tietze,et al.  Enantioselective Total Synthesis of a Natural Norsesquiterpene of the Calamenene Group by a Silane-Terminated Intramolecular Heck Reaction , 1995 .

[48]  J. Fiaud,et al.  PALLADIUM-CATALYZED ASYMMETRIC HYDROPHENYLATION OF 1,4-DIHYDRO-1,4-EPOXYNAPHTHALENE , 1995 .

[49]  M. Shibasaki,et al.  Asymmetric Heck reaction: A catalytic asymmetric synthesis of the key intermediate of (−)-oppositol and (−)-prepinnaterpene , 1995 .

[50]  A. Meyers,et al.  Asymmetric Synthesis of the Key Intermediates Leading to (-)-Aphanorphine and (-)-Eptazocine , 1995 .

[51]  Barry M. Trost,et al.  Atom Economy—A Challenge for Organic Synthesis: Homogeneous Catalysis Leads the Way , 1995 .

[52]  R. Larock,et al.  Enantioselective, Palladium-Catalyzed Hetero- and Carboannulation of Allenes Using Functionally-Substituted Aryl and Vinylic Iodides , 1995 .

[53]  A. Meijere,et al.  Fine Feathers Make Fine Birds: The Heck Reaction in Modern Garb† , 1995 .

[54]  M. Sodeoka,et al.  Regio- and Stereoselective Functionalization of an Optically Active Tetrahydroindolizine Derivative. Catalytic Asymmetric Syntheses of Lentiginosine, 1,2-Diepilentiginosine, and Gephyrotoxin 209D , 1995 .

[55]  John M. Brown,et al.  Stable Arylpalladium Iodides and Reactive Arylpalladium Trifluoromethanesulfonates in the Intramolecular Heck Reaction , 1995 .

[56]  J. Tsuji,et al.  Palladium Reagents and Catalysts , 1995 .

[57]  M. Sodeoka,et al.  Effects of Solvents and Additives in the Asymmetric Heck Reaction of Alkenyl Triflates: Catalytic Asymmetric Synthesis of Decalin Derivatives and Determination of the Absolute Stereochemistry of (+)-Vernolepin , 1994 .

[58]  M. Sodeoka,et al.  Asymmetric Heck-Type Reaction Utilizing Hypervalent Alkenyliodonium Salt , 1994 .

[59]  M. Sodeoka,et al.  Asymmetric Heck Reaction : Catalytic Asymmetric Syntheses of Bioactive Molecules , 1994 .

[60]  S. Weinreb,et al.  Consecutive carbon-carbon bond formation via the π-allylpalladium variant of the Heck reaction , 1994 .

[61]  L. Tietze,et al.  Regio‐ and Enantioselective Silane‐Terminated Intramolecular Heck Reactions , 1994 .

[62]  I. Goldberg,et al.  Phorbazoles AD, novel chlorinated phenylpyrrolyloxazoles from the marine sponge phorbas aff. clathrata , 1994 .

[63]  M. Sodeoka,et al.  Palladium-catalyzed asymmetric arylation of 4,7-dihydro-1,3-dioxepin. Catalytic asymmetric synthesis of γ-butyrolactone derivatives , 1994 .

[64]  M. Sodeoka,et al.  Asymmetric heck reaction of alkenyl iodides in the presence of silver salts. Catalytic asymmetric synthesis of decalin and functionalized indolizidine derivatives , 1994 .

[65]  L. Overman Application of intramolecular Heck reactions for forming congested quaternary carbon centers in complex molecule total synthesis , 1994 .

[66]  F. Ozawa,et al.  Palladium-catalysed asymmetric hydroalkenylation of norbornene , 1994 .

[67]  S. Sakuraba,et al.  Asymmetric Heck-type Hydroarylation of Norbornene with Phenyl Triflate Catalyzed by Palladium Complexes of Chiral (β-N-Sulfonylaminoalkyl)phosphines1 , 1994 .

[68]  L. Overman,et al.  Catalytic asymmetric synthesis of either enantiomer of physostigmine. Formation of quaternary carbon centers with high enantioselection by intramolecular Heck reactions of (Z)-2-butenanilides , 1993 .

[69]  K. Yanagi,et al.  Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with phenyl triflate. A novel asymmetric catalysis involving a kinetic resolution process , 1993 .

[70]  K. Fuji,et al.  Asymmetric creation of quaternary carbon centers , 1993 .

[71]  M. Sodeoka,et al.  Catalytic asymmetric synthesis of benzylic quaternary carbon centers. An efficient synthesis of (-)-eptazocine , 1993 .

[72]  O. Reiser,et al.  Palladium Catalyzed Coupling Reactions of 2,3-Dihydrofuran Using High Pressure Conditions , 1993 .

[73]  M. Sodeoka,et al.  Catalytic asymmetric synthesis of a functionalized indolizidine derivative. A useful intermediate suitable for the synthesis of various glycosidase inhibitors , 1993 .

[74]  M. Sodeoka,et al.  Asymmetric heck reaction. A catalytic asymmetric synthesis of the key intermediate for vernolepin , 1993 .

[75]  F. Ozawa,et al.  Palladium-catalyzed asymmetric alkenylation of cyclic olefins , 1993 .

[76]  Chris P. Miller,et al.  Stereospecific synthesis of peptide analogs with allo-threonine and D-allo-threonine residues , 1993 .

[77]  M. Shibasaki,et al.  Asymmetric heck reaction-anion capture process. A catalytic asymmetric synthesis of the key intermediates for the Capnellenols , 1993 .

[78]  L. Tietze,et al.  Sequential Transformations in Organic Chemistry: A Synthetic Strategy with a Future† , 1993 .

[79]  M. Sodeoka,et al.  Asymmetric Heck Reaction: Catalytic Asymmetric Syntheses of Bicyclic Enones, Dienones and the Key Intermediate for Vernolepin , 1993 .

[80]  S. Takano,et al.  A facile route to the aromatic bisabolane sesquiterpenes by homobenzylic-homoallylic hydrogenolysis , 1993 .

[81]  Y. Kondo,et al.  The palladium-catalyzed arylation of 4H-1,3-dioxin , 1992 .

[82]  Chris P. Miller,et al.  An investigation of the mitsunobu reaction in the preparation of peptide oxazolines, thiazolines, and aziridines , 1992 .

[83]  L. Overman,et al.  Catalytic asymmetric synthesis of quarternary carbon centers. Palladium-catalyzed formation of either enantiomer of spirooxindoles and related spirocyclics using a single enantiomer of a chiral diphosphine ligand , 1992 .

[84]  M. Shibasaki,et al.  A catalytic asymmetric synthesis of hydrindans , 1992 .

[85]  F. Ozawa,et al.  Catalytic asymmetric arylation of N-substituted 2-pyrrolines with aryl triflates , 1992 .

[86]  M. Shibasaki,et al.  Further studies on a catalytic asymmetric synthesis of decalin derivatives , 1992 .

[87]  C. J. Elsevier,et al.  Influence of ligands and anions on the rate of carbon monoxide insertion into palladium-methyl bonds in the complexes (P-P)Pd(CH3)Cl and [(P-P)Pd(CH3)(L)]+SO3CF3- (P-P = dppe, dppp, dppb, dppf; L = CH3CN, PPh3) , 1992 .

[88]  F. Ozawa,et al.  Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran: 1,8-Bis(dimethylamino)naphthalene as an efficient base , 1992 .

[89]  W. Cabri,et al.  .alpha.-Regioselectivity in palladium-catalyzed arylation of acyclic enol ethers , 1992 .

[90]  Akihiko Kubo,et al.  Catalytic asymmetric arylation of olefins , 1992 .

[91]  R. D. Santo,et al.  Heck reaction on anthraquinone derivatives: ligand, solvent and salt effects , 1991 .

[92]  M. Shibasaki,et al.  Asymmetric Heck reaction: a catalytic asymmetric synthesis of the key intermediate for .DELTA.9(12)-capnellene-3.beta.,8.beta.,10.alpha.-triol and .DELTA.9(12)-capnellene-3.beta.,8.beta.,10.alpha.,14-tetrol , 1991 .

[93]  F. Ozawa,et al.  Catalytic asymmetric arylation of 2,3-dihydrofuran with aryl triflates , 1991 .

[94]  R. Grigg,et al.  Suppression of alkene isomerisation in products from intramolecular heck reactions by addition of Tl(1) salts. , 1991 .

[95]  H. Brunner,et al.  Asymmetric Catalysis. 72.1 Enantioselective Hydroarylation of Norbornene and Norbornadiene with Palladium(II) Acetate/Phosphine Catalysts , 1991 .

[96]  M. Sodeoka,et al.  On the Role of Silver Salts in Asymmetric Heck-type Reaction. A Greatly Improved Catalytic Asymmetric Synthesis of cis-Decalin Derivatives , 1990 .

[97]  L. Overman,et al.  Palladium-catalyzed polyene cyclizations of trienyl triflates , 1989 .

[98]  M. Sodeoka,et al.  Catalytic asymmetric carbon-carbon bond formation: asymmetric synthesis of cis-decalin derivatives by palladium-catalyzed cyclization of prochiral alkenyl iodides , 1989 .

[99]  Tamio Hayashi,et al.  Palladium-catalyzed asymmetric 1,4-disilylation of .alpha.,.beta.-unsaturated ketones: catalytic asymmetric synthesis of .beta.-hydroxy ketones , 1988 .

[100]  K. Sharpless,et al.  Asymmetric synthesis of both enantiomers of tomoxetine and fluoxetine. Selective reduction of 2,3-epoxycinnamyl alcohol with Red-Al , 1988 .

[101]  Qian-sheng Yu,et al.  Practical synthesis of unnatural (+)-physostigmine and carbamate analogues , 1988 .

[102]  M. Abelman,et al.  Intramolecular alkene arylations for rapid assembly of polycyclic systems containing quaternary centers. A new synthesis of spirooxindoles and other fused and bridged ring systems , 1987 .

[103]  T. Masamune,et al.  Synthesis of (±)-prepinnaterpene, a bromoditerpene from the red alga Laurencia Pinnata Yamada , 1987 .

[104]  S. Ikegami,et al.  The first total syntheses of .DELTA.9(12)-Capnellene-8.beta.,10.alpha.-diol and .DELTA.9(12)-capnellene-3.beta.,8.beta.,10.alpha.-triol , 1986 .

[105]  C. Westerlund,et al.  The effect of added silver nitrate on the palladium-catalyzed arylation of allyltrimethylsilanes , 1985 .

[106]  R. Heck Palladium reagents in organic syntheses , 1985 .

[107]  V. Bierbaum,et al.  Gas-phase reactions of organic anions as studied by the flowing afterglow technique , 1981 .

[108]  R. Heck Palladium-catalyzed reactions of organic halides with olefins , 1979 .

[109]  T. Kitahara,et al.  The total synthesis of dl-vernolepin and dl-vernomenin , 1977 .

[110]  M. Kumada,et al.  A chiral (hydroxyalkylferrocenyl)phosphine ligand. Highly stereoselective catalytic asymmetric hydrogenation of prochiral carbonyl compounds , 1976 .

[111]  R. Heck,et al.  Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides , 1972 .

[112]  K. Mori,et al.  Arylation of Olefin with Aryl Iodide Catalyzed by Palladium , 1971 .

[113]  Richard F. Heck,et al.  Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives , 1968 .