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Pablo Espinet - One of the best experts on this subject based on the ideXlab platform.
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the Stille Reaction 38 years later
ACS Catalysis, 2015Co-Authors: Carlos Cordovilla, Camino Bartolome, Jesus M Martinezilarduya, Pablo EspinetAbstract:The first now-named Stille Reaction was published 38 years ago, and the last comprehensive revision of this catalysis was in 2004. Since then, the knowledge of the different steps of the three possible (and sometimes competing) Reaction pathways (cyclic, open, and ionic) has been almost completed by synergistic experimental and theoretical studies: the Stille Reaction is perhaps the best characterized catalytic process if we consider the number of intermediates that have been detected. This review concentrates on the mechanistic new knowledge and on important aspects such as the revolution with the use of bulky phosphines, the bimetallic alternative of the Stille Reaction, the enantioselectivity in Stille and palladium-free Stille processes, the meaning of copper effect, or the possible approaches to make Stille coupling a greener process.
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Fluorene-based stannylated polymers and their use as recyclable reagents in the Stille Reaction
Journal of Organometallic Chemistry, 2011Co-Authors: Nora Carrera, Pablo Espinet, Alfonso Salinas-castillo, Ana C. Albéniz, Ricardo MallaviaAbstract:Abstract Stannylated polymers based on the polyfluorene backbone have been synthesized and used in the Stille Reaction as recyclable reagents, minimizing the generation of toxic tin residues.
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Stille coupling of alkynyl stannane and aryl iodide a many pathways Reaction the importance of isomerization
Organometallics, 2011Co-Authors: Monica H Pereztemprano, Ana M. Gallego, Juan A Casares, Pablo EspinetAbstract:The kinetics of the Stille Reaction between C6Cl2F3I and PhCCSnBu3 have been studied for the whole catalytic system and for transmetalations as separate steps. The use of (trifluorodichlorophenyl)palladium derivatives slows down the Reactions and allows for the observation of the intermediates cis- and trans-[Pd(C6Cl2F3)I(PPh3)2]. The first is formed in the oxidative addition step and isomerizes to the second. Both were studied as catalysts for the whole cycle. The kinetic study compares the relevance of the transmetalation step on each isomer. The competing transmetalations produce both cis- and trans-[Pd(C6Cl2F3)(PhCC)(PPh3)2]. The former undergoes very fast C−C coupling, while the second accumulates in solution due to extremely slow isomerization. Thus, the system is a case study of the effect of competing pathways in the Stille Reaction and its consequences on the performance of the catalytic process.
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selective green coupling of alkynyltins and allylic halides to trienynes via a tandem double Stille Reaction
Advanced Synthesis & Catalysis, 2010Co-Authors: Isabel Meana, Ana C. Albéniz, Pablo EspinetAbstract:The palladium-catalyzed Reaction of alkynyltin compounds with allylic chlorides leads to a 2:2 coupling to give trienynes by regio- and stereoselective formation of three new C-C bonds. The Reaction can be applied to different alkynyl and allylic fragments, providing a wide range of trienynes with different substitution patterns in very good yields. They can be prepared in a green way using recyclable polymeric tin alkynyls.
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Stannylated Polynorbornenes as New Reagents for a Clean Stille Reaction
Chemistry: A European Journal, 2008Co-Authors: Nora Carrera, Ana C. Albéniz, Enrique Gutiérrez, Rut Benavente, M. Mar Villavieja, Pablo EspinetAbstract:: New functionalized polynorbornenes have been obtained in good yields by vinylic copolymerization of norbornene with a (norbornenyl)SnBu(2)Cl monomer, catalyzed by [Ni(C(6)F(5))(2)(SbPh(3))(2)]. Subsequent functionalization produces a wide variety of polymers with different --SnBu(2)R groups (R=aryl, vinyl, alkynyl). The polymers can be used as R-transfer reagents in Stille couplings, thereby providing easy workup and separation of the polymeric tin byproducts from the coupling products. Tin contents of around 0.05 wt % are found in the Stille products. The stannylated polymers can be recycled and reused with good efficiency.
David J. Sinclair - One of the best experts on this subject based on the ideXlab platform.
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Mini Review The intramolecular Stille Reaction in some target natural product syntheses
2020Co-Authors: Gerald Pattenden, David J. SinclairAbstract:Abstract A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for theintramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, theamphidinolides, lophotoxin, and pateamine, is described. © 2002 Elsevier Science B.V. All rights reserved. Keywords :Stille Reaction; Macrolactones; Macrolactams 1. Introduction The palladium(0)-catalysed Stille coupling Reactionbetween an organostannane reagent and an organicelectrophile has become one of the revered methods forthe synthesis of 1,3-dienes and other conjugated polye-nes in contemporary organic synthesis [1–3]. Over thepast decade, developments and applications of thescope for the Reaction in the synthesis of complexmacrocyclic structures of natural origin have been re-ally quite awesome [4,5]. A few years ago, we captureda flavour of the momentum in this area in a review ofthe applications of the intramolecular Stille Reaction [6].At the same time, we surveyed the range of methodsavailable for the synthesis of the organostannane andelectrophile components used in the Reaction. Our re-search group in Nottingham has been particularly inter-ested in exploring the scope for the intramolecular StilleReaction in the synthesis of macrocyclic constructs foralmost a decade, and we would like to believe that wehave contributed in a significant way in this area. As atribute to the late J.K. Stille, we now present a person-alised and chronological summary of the contributionswe have made to exposing the scope of the intramolec-ular Stille Reaction in target macrocycles of particularbiological interest to us over the past decade.
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the intramolecular Stille Reaction in some target natural product syntheses
Journal of Organometallic Chemistry, 2002Co-Authors: Gerald Pattenden, David J. SinclairAbstract:A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for the intramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, the amphidinolides, lophotoxin, and pateamine, is described.
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The intramolecular Stille Reaction in some target natural product syntheses
Journal of Organometallic Chemistry, 2002Co-Authors: Gerald Pattenden, David J. SinclairAbstract:A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for the intramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, the amphidinolides, lophotoxin, and pateamine, is described. © 2002 Elsevier Science B.V. All rights reserved.
Mohamed Abarbri - One of the best experts on this subject based on the ideXlab platform.
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Regioselective Synthesis of (E)-5-(Tributylstannylmethylidene)-5H-furan-2-ones and (E)-3-(Tributylstannylmethylidene)-3H-isobenzofuran-1-ones: Easy Access to γ-Alkylidenebutenolide and Phthalide Skeletons
Synthesis, 2007Co-Authors: Alain Duchene, Jerome Thibonnet, Jeanluc Parrain, Elsa Anselmi, Mohamed AbarbriAbstract:Regio- and stereoselective synthesis of γ-alkylidenebutenolides and y-alkylidenephthalides has been achieved through the palladium-catalysed tandem cross-coupling/cyclisation Reactions oftributylstannyl-3-iodopropenoate or the 2-iodo benzoate derivatives with tributyltinacetylene. Iododestannylation occurred with inversion of the configuration of the exocyclic double bond in the case of butenolides, but with retention of configuration for the phthalide. The selectivity observed in the Stille Reaction was found to be dependent on the nature of the vinyl or the aryl halide.
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Regioselective Synthesis of 1,4,6-Trisubstituted-2-Pyridinones and 2,3-Disubstituted (2H)-Isoquinolin-1-ones via Tandem Stille Reaction/Heterocyclisation
Synthesis, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to 1,4,6-trisubstituted 2-pyridinones and 2,3-disubstituted (2H)-isoquinolin-1-ones from (Z)-3-iodovinylic amides la-h and 2-iodo N-substituted benzamides 2a-f is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic amides la-h and 2-iodobenzamides 2a-f with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine and tetrabutylammonium bromide in acetonitrile provided good yields of the corresponding 1,4,6-trisubstituted 2-pyridinones 3a-k and 2,3-disubstituted (2H)-isoquinolin-1-ones 4a-i via tandem Stille Reaction and 6-endo-dig azacyclisation.
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Synthesis of Isocoumarins and α-Pyrones via Tandem Stille Reaction/Heterocyclization
Journal of Organic Chemistry, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to α-pyrones and 3-substituted isocoumarins from (Z)-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine, and tetrabutylammonium bromide in dimethylformamide provided good yields of the corresponding α-pyrones 3a−k or 3-substituted isocoumarins 5a−g via tandem Stille Reaction and 6-endo-dig oxacyclization.
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synthesis of isocoumarins and α pyrones via tandem Stille Reaction heterocyclization
Journal of Organic Chemistry, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to α-pyrones and 3-substituted isocoumarins from (Z)-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine, and tetrabutylammonium bromide in dimethylformamide provided good yields of the corresponding α-pyrones 3a−k or 3-substituted isocoumarins 5a−g via tandem Stille Reaction and 6-endo-dig oxacyclization.
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Regio- and selective synthesis of 4,6-disubstituted-2-pyridones
Tetrahedron Letters, 2003Co-Authors: Khalil Cherry, Mohamed Abarbri, Jeanluc Parrain, Alain DucheneAbstract:Abstract Palladium catalysed regio- and stereoselective annulation of allenyl stannanes by β-iodo vinylic amides gives good yields of the corresponding 2-pyridones. This annulation probably occurs via a Stille Reaction/cyclisation sequence.
Alain Duchene - One of the best experts on this subject based on the ideXlab platform.
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Regioselective Synthesis of (E)-5-(Tributylstannylmethylidene)-5H-furan-2-ones and (E)-3-(Tributylstannylmethylidene)-3H-isobenzofuran-1-ones: Easy Access to γ-Alkylidenebutenolide and Phthalide Skeletons
Synthesis, 2007Co-Authors: Alain Duchene, Jerome Thibonnet, Jeanluc Parrain, Elsa Anselmi, Mohamed AbarbriAbstract:Regio- and stereoselective synthesis of γ-alkylidenebutenolides and y-alkylidenephthalides has been achieved through the palladium-catalysed tandem cross-coupling/cyclisation Reactions oftributylstannyl-3-iodopropenoate or the 2-iodo benzoate derivatives with tributyltinacetylene. Iododestannylation occurred with inversion of the configuration of the exocyclic double bond in the case of butenolides, but with retention of configuration for the phthalide. The selectivity observed in the Stille Reaction was found to be dependent on the nature of the vinyl or the aryl halide.
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Regioselective Synthesis of 1,4,6-Trisubstituted-2-Pyridinones and 2,3-Disubstituted (2H)-Isoquinolin-1-ones via Tandem Stille Reaction/Heterocyclisation
Synthesis, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to 1,4,6-trisubstituted 2-pyridinones and 2,3-disubstituted (2H)-isoquinolin-1-ones from (Z)-3-iodovinylic amides la-h and 2-iodo N-substituted benzamides 2a-f is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic amides la-h and 2-iodobenzamides 2a-f with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine and tetrabutylammonium bromide in acetonitrile provided good yields of the corresponding 1,4,6-trisubstituted 2-pyridinones 3a-k and 2,3-disubstituted (2H)-isoquinolin-1-ones 4a-i via tandem Stille Reaction and 6-endo-dig azacyclisation.
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Synthesis of Isocoumarins and α-Pyrones via Tandem Stille Reaction/Heterocyclization
Journal of Organic Chemistry, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to α-pyrones and 3-substituted isocoumarins from (Z)-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine, and tetrabutylammonium bromide in dimethylformamide provided good yields of the corresponding α-pyrones 3a−k or 3-substituted isocoumarins 5a−g via tandem Stille Reaction and 6-endo-dig oxacyclization.
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synthesis of isocoumarins and α pyrones via tandem Stille Reaction heterocyclization
Journal of Organic Chemistry, 2005Co-Authors: Khalil Cherry, Jerome Thibonnet, Jeanluc Parrain, Alain Duchene, Mohamed AbarbriAbstract:A general route to α-pyrones and 3-substituted isocoumarins from (Z)-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c is described, including compounds bearing a substituent on the aromatic ring. Treatment of (Z)-β-iodovinylic acids 1a−f or 2-iodobenzoic acids 4a−c with various allenyltributyltin reagents in the presence of palladium acetate, triphenylphosphine, and tetrabutylammonium bromide in dimethylformamide provided good yields of the corresponding α-pyrones 3a−k or 3-substituted isocoumarins 5a−g via tandem Stille Reaction and 6-endo-dig oxacyclization.
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Regio- and selective synthesis of 4,6-disubstituted-2-pyridones
Tetrahedron Letters, 2003Co-Authors: Khalil Cherry, Mohamed Abarbri, Jeanluc Parrain, Alain DucheneAbstract:Abstract Palladium catalysed regio- and stereoselective annulation of allenyl stannanes by β-iodo vinylic amides gives good yields of the corresponding 2-pyridones. This annulation probably occurs via a Stille Reaction/cyclisation sequence.
Gerald Pattenden - One of the best experts on this subject based on the ideXlab platform.
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Mini Review The intramolecular Stille Reaction in some target natural product syntheses
2020Co-Authors: Gerald Pattenden, David J. SinclairAbstract:Abstract A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for theintramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, theamphidinolides, lophotoxin, and pateamine, is described. © 2002 Elsevier Science B.V. All rights reserved. Keywords :Stille Reaction; Macrolactones; Macrolactams 1. Introduction The palladium(0)-catalysed Stille coupling Reactionbetween an organostannane reagent and an organicelectrophile has become one of the revered methods forthe synthesis of 1,3-dienes and other conjugated polye-nes in contemporary organic synthesis [1–3]. Over thepast decade, developments and applications of thescope for the Reaction in the synthesis of complexmacrocyclic structures of natural origin have been re-ally quite awesome [4,5]. A few years ago, we captureda flavour of the momentum in this area in a review ofthe applications of the intramolecular Stille Reaction [6].At the same time, we surveyed the range of methodsavailable for the synthesis of the organostannane andelectrophile components used in the Reaction. Our re-search group in Nottingham has been particularly inter-ested in exploring the scope for the intramolecular StilleReaction in the synthesis of macrocyclic constructs foralmost a decade, and we would like to believe that wehave contributed in a significant way in this area. As atribute to the late J.K. Stille, we now present a person-alised and chronological summary of the contributionswe have made to exposing the scope of the intramolec-ular Stille Reaction in target macrocycles of particularbiological interest to us over the past decade.
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the intramolecular Stille Reaction in some target natural product syntheses
Journal of Organometallic Chemistry, 2002Co-Authors: Gerald Pattenden, David J. SinclairAbstract:A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for the intramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, the amphidinolides, lophotoxin, and pateamine, is described.
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A concise enantioselective total synthesis of rhizoxin D
Tetrahedron Letters, 2002Co-Authors: Ian S. Mitchell, Gerald Pattenden, Jeffrey StonehouseAbstract:Abstract A new and convergent synthesis of the antitumour macrolide rhizoxin D 2 is described. The synthesis features a Wadsworth–Emmons olefination and a facile intramolecular Stille Reaction to elaborate the 16-membered macrocyclic core 5 from the vinyl iodide 3 and the vinyl stannane 4 as key steps.
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The intramolecular Stille Reaction in some target natural product syntheses
Journal of Organometallic Chemistry, 2002Co-Authors: Gerald Pattenden, David J. SinclairAbstract:A chronological summary of the contributions made by researchers in Nottingham, UK, to developing the scope for the intramolecular Stille Reaction in target natural product syntheses, e.g. leinamycin, the virginiamycins, macrolactin A, rhizoxin, the amphidinolides, lophotoxin, and pateamine, is described. © 2002 Elsevier Science B.V. All rights reserved.
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The intramolecular Stille Reaction
Journal of the Chemical Society Perkin Transactions 1, 1999Co-Authors: Matthew Alexander James Duncton, Gerald PattendenAbstract:A review with 80 refs. including prepns. of macrocycles. [on SciFinder(R)]
