醇脱水是合成烯烃的重要方法之一。全球每年约有15%的苯乙烯是通过1-苯乙醇在酸性条件下脱水反应生产。虽然人们对该反应进行了较为深入的研究,但是当使用活性较高的1-苯乙醇衍生物为底物时,由于得到的取代苯乙烯产物具有较高的反应性,在脱水过程中会发生聚合而导致反应选择性降低,因此有必要探索适宜在高活性1-苯基乙醇脱水反应中应用的催化剂体系。
本文借助酸碱协同催化方法考察了1-(4-甲氧基苯基)乙醇制备4-甲氧基苯乙烯的反应。发现三苯基磷与 AlCl3构建的 Lewis碱/Lewis酸协同催化体系在硝基甲烷中可以接近定量的收率得到4-甲氧基苯乙烯。 Lewis碱/Lewis酸协同催化体系有效避免了4-甲氧基苯乙烯的二聚现象。底物拓展研究显示该方法具有很好的底物普适性,对多种取代苯乙烯的收率均超过80%。机理研究表明,1-(4-甲氧基苯基)乙醇在酸作用下先生成碳正离子,三苯基磷作为偶极性的电子给体不但能在一定程度上稳定该苄基碳正离子,而且抑制了其与4-甲氧基苯乙烯之间的亲电反应,进而最大化了脱质子生成4-甲氧基苯乙烯的选择性。
将Lewis碱协助的 Lewis酸催化提高反应选择性策略用于2-苯基-3,4-二氢吡喃衍生物合成2-肉桂基-1,3-二羰基化合物的开环反应。该类取代二氢吡喃在酸催化剂作用下也可生成苄基碳正离子,但是该中间体易受分子间和分子内亲电反应影响,反应选择性不高。而当使用单质碘/三苯基磷协同催化体系时,2-苯基-3,4-二氢吡喃衍生物能高选择性地实现开环反应,得到反式2-肉桂基-1,3-二羰基化合物。该类1,3-二羰基化合物具有丰富的反应性,是一类重要的合成子。
Acid‐catalyzed dehydration of alcohols has been widely employed for the synthesis of alkenes. However, activated alcohols when employed as substrates in dehydration reactions are often plagued by the lack of alkene selectivity. In this work, the reaction system can be significantly im‐proved through enhancing the performance of Lewis acid catalysts in the dehydration of activated alcohols by combining with a Lewis base. Observations of the reaction mechanism revealed that the Lewis base component might have changed the reaction rate order. Although both the principal and side reaction rates decreased, the effect was markedly more observed on the latter reaction. There‐fore, the selectivity of the dehydration reaction was improved. On the basis of this observation, a new route to synthesize 2‐cinnamyl‐1,3‐dicarbonyl compounds was developed by using 2‐aryl‐3,4‐dihydropyran as a starting substrate in the presence of a Lewis acid/Lewis base combined catalyst system.
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