Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Chemistry. 2012 Feb 20;18(8):2423-9. doi: 10.1002/chem.201103009. Epub 2012 Jan 16.
We present herein a versatile and broadly applicable Fe-catalyzed regioselective alkoxy allylation of activated double bonds. Substituted allylic carbonates are converted into the corresponding σ-enyl Fe complexes by reaction with Bu(4)N[Fe(CO)(3)(NO)] (TBAFe) at 30 °C. The liberated alkoxide adds to an activated double bond with the generation of a C-nucleophile, which is trapped by the σ-enyl Fe complex in a regioselective manner. Alternatively, the alkoxide acts as a base in deprotonating an external pronucleophile, which undergoes Michael addition. The method is characterized by a broad functional group tolerance, mild reaction conditions, low catalyst loadings, and high regioselectivities in favor of the ipso-substitution product.
我们在此提出了一种多功能且广泛适用的 Fe 催化的活性双键区域选择性烷氧基烯丙基化反应。取代的烯丙基碳酸酯与 Bu(4)N[Fe(CO)(3)(NO)] (TBAFe) 在 30°C 下反应，生成相应的 σ-烯基 Fe 配合物。释放出的烷氧基与活性双键加成，生成 C-亲核试剂，该亲核试剂被 σ-烯基 Fe 配合物以区域选择性方式捕获。或者，烷氧基作为碱去质子化外部给电子体，随后发生迈克尔加成。该方法具有广泛的官能团容忍性、温和的反应条件、低催化剂负载量以及有利于 ipso-取代产物的高区域选择性等特点。
