Gregson Charlotte H U, Ganesh Venkataraman, Aggarwal Varinder K
School of Chemistry , University of Bristol , Cantock's Close, Bristol BS8 1TS , U.K.
Org Lett. 2019 May 3;21(9):3412-3416. doi: 10.1021/acs.orglett.9b01152. Epub 2019 Apr 24.
The reactivity of boronate complexes which resemble donor-acceptor cyclopropanes is described. The enantioenriched cyclopropyl boronate complexes were shown to undergo concerted 1,2-metalate rearrangement/ring opening upon activation with a Lewis acid. This method provides atom-efficient access to optically active γ-carbonyl boronic esters in moderate to excellent yields with complete enantiospecificity. Furthermore, a three-component variant of the reaction was established through in situ alkylation, and the synthetic utility of the products as chiral building blocks was demonstrated.
描述了类似于给体-受体环丙烷的硼酸酯配合物的反应活性。结果表明，对映体富集的环丙基硼酸酯配合物在用路易斯酸活化后会发生协同的1,2-金属化重排/开环反应。该方法以中等至优异的产率和完全的对映体特异性，提供了原子经济性地获得光学活性γ-羰基硼酸酯的途径。此外，通过原位烷基化建立了该反应的三组分变体，并证明了产物作为手性砌块的合成效用。
