Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg , Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
J Am Chem Soc. 2014 Jan 15;136(2):777-82. doi: 10.1021/ja4110842. Epub 2014 Jan 6.
Novel allyl boron compounds are readily synthesized via rearrangement reactions between Lewis acidic B(C6F5)3 and propargyl esters. These reactions proceed through an initial cyclization followed by ring-opening and concurrent C6F5-group migration. In the absence of disubstitution adjacent to the ester oxygen atom, an allyl boron migration rearrangement leads to formal 1,3-carboboration products. These allyl boron compounds act as allylation reagents with aldehydes introducing both a C3-allyl fragment and a C6F5-unit as a single anti-diastereomer. In these reactions, B(C6F5)3 activates the alkynes, prompting the rearrangement processes and enabling installations of C6F5 and R-groups.
新型烯丙基硼化合物可通过路易斯酸性 B(C6F5)3 和丙炔酸酯之间的重排反应轻易合成。这些反应首先经历环化，随后开环并伴随 C6F5 基团迁移。如果酯氧原子邻位没有取代，则烯丙基硼迁移重排会导致形成 1,3-碳硼化产物。这些烯丙基硼化合物作为烯丙基化试剂与醛反应，作为单一的反式非对映异构体引入 C3-烯丙基片段和 C6F5 单元。在这些反应中，B(C6F5)3 激活炔烃，促使重排过程发生，并实现 C6F5 和 R 基团的安装。
