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
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