Flow Chemistry Syntheses of Styrenes, Unsymmetrical Stilbenes and Branched Aldehydes

被引:61
作者
Bourne, Samuel L. [1 ]
O'Brien, Matthew [2 ]
Kasinathan, Sivarajan [3 ]
Koos, Peter [1 ]
Tolstoy, Paeivi [1 ]
Hu, Dennis X. [1 ]
Bates, Roderick W. [3 ]
Martin, Benjamin [4 ]
Schenkel, Berthold [4 ]
Ley, Steven V. [1 ]
机构
[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
[2] Keele Univ, Sch Phys & Geog Sci, Keele ST5 5BG, Staffs, England
[3] Nanyang Technol Univ, Div Chem & Biol Chem, Sch Phys & Math Sci, Singapore 637371, Singapore
[4] Novartis Pharma AG, Chem & Analyt Dev, Werk Klybeck, CH-4057 Basel, Switzerland
基金
英国工程与自然科学研究理事会;
关键词
aldehydes; flow chemistry; hydroformylation; unsymmetrical stilbenes; vinylation; RHODIUM-CATALYZED HYDROFORMYLATION; CROSS-COUPLING REACTIONS; SUZUKI-MIYAURA REACTION; HECK REACTIONS; ORGANIC-SYNTHESIS; ARYL BROMIDES; REGIOSELECTIVE HYDROFORMYLATION; POTASSIUM VINYLTRIFLUOROBORATE; ASYMMETRIC-SYNTHESIS; PALLADIUM;
D O I
10.1002/cctc.201200778
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Two tandem flow chemistry processes have been developed. A single palladium-catalysed Heck reaction with ethylene gas provides an efficient synthesis for functionalised styrenes. Through further elaboration the catalyst becomes multi-functional and performs a second Heck reaction providing a single continuous process for the synthesis of unsymmetrical stilbenes. In addition, the continuous, rhodium-catalysed, hydroformylation of styrene derivatives with syngas affords branched aldehydes with good selectivity. Incorporation of an in-line aqueous wash and liquid-liquid separation allowed for the ethylene Heck reaction to be telescoped into the hydroformylation step such that a single flow synthesis of branched aldehydes directly from aryl iodides was achieved. The tube-in-tube semi-permeable membrane-based gas reactor and liquid-liquid separator both play an essential role in enabling these telescoped flow processes.
引用
收藏
页码:159 / 172
页数:14
相关论文
共 113 条
  • [81] Mizoroki-Heck Reactions Catalyzed by Dichloro{bis[1-(dicyclohexylphosphanyl)piperidine]}palladium: Palladium Nanoparticle Formation Promoted by (Water-Induced) Ligand Degradation
    Oberholzer, Miriam
    Gerber, Roman
    Frech, Christian M.
    [J]. ADVANCED SYNTHESIS & CATALYSIS, 2012, 354 (04) : 627 - 641
  • [82] 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
    OHRAI, K
    KONDO, K
    SODEOKA, M
    SHIBASAKI, M
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (26) : 11737 - 11748
  • [83] The Oxygen-Mediated Synthesis of 1,3-Butadiynes in Continuous Flow: Using Teflon AF-2400 to Effect Gas/Liquid Contact
    Petersen, Trine P.
    Polyzos, Anastasios
    O'Brien, Matthew
    Ulven, Trond
    Baxendale, Ian R.
    Ley, Steven V.
    [J]. CHEMSUSCHEM, 2012, 5 (02) : 274 - 277
  • [84] Suzuki cross-coupling reactions between alkenylboronic acids and aryl bromides catalysed by a tetraphosphane-palladium catalyst
    Peyroux, E
    Berthiol, F
    Doucet, H
    Santelli, M
    [J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2004, 2004 (05) : 1075 - 1082
  • [85] PALLADIUM-CATALYZED ARYLATION OF ETHYLENE
    PLEVYAK, JE
    HECK, RF
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1978, 43 (12) : 2454 - 2460
  • [86] REGIOSELECTIVE HYDROFORMYLATION OF CYCLIC VINYL AND ALLYL ETHERS WITH RHODIUM CATALYSTS - CRUCIAL INFLUENCE OF THE SIZE OF THE PHOSPHORUS COCATALYST
    POLO, A
    CLAVER, C
    CASTILLON, S
    RUIZ, A
    BAYON, JC
    REAL, J
    MEALLI, C
    MASI, D
    [J]. ORGANOMETALLICS, 1992, 11 (11) : 3525 - 3533
  • [87] The Continuous-Flow Synthesis of Carboxylic Acids using CO2 in a Tube-In-Tube Gas Permeable Membrane Reactor
    Polyzos, Anastasios
    O'Brien, Matthew
    Petersen, Trine P.
    Baxendale, Ian R.
    Ley, Steven V.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (05) : 1190 - 1193
  • [88] A reliable multikilogram-scale synthesis of 2-acetamido-5-vinylpyridine using catalytic BINAP in a modified Heck reaction
    Raggon, JW
    Snyder, WM
    [J]. ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2002, 6 (01) : 67 - 69
  • [89] Continuous Flow Organic Synthesis under High-Temperature/Pressure Conditions
    Razzaq, Tahseen
    Kappe, C. Oliver
    [J]. CHEMISTRY-AN ASIAN JOURNAL, 2010, 5 (06) : 1274 - 1289
  • [90] Ligand-free Heck reactions using low Pd-loading
    Reetz, MT
    de Vries, JG
    [J]. CHEMICAL COMMUNICATIONS, 2004, (14) : 1559 - 1563