Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, Tamil Nadu, India.
Chem Asian J. 2019 Dec 13;14(24):4549-4552. doi: 10.1002/asia.201900820. Epub 2019 Jul 24.
An oxidative trifunctionalization of aryl alkynoates has been devised via the chalcogenide radical triggered intramolecular 1,4-aryl migration/decarboxylation cascade to prepare 1,1-dichalcogenide tetrasubstituted alkenes in high yields (up to 98 %). This operationally simple reaction proceeds under metal-free conditions, can be executed on gram scale, and highlights formal 1,1-difunctionalization of alkynes. Synthetic potential of this protocol was demonstrated through a twofold cascade rearrangement to access highly conjugated tetra-selenylated alkenes along with a cross-dehydrogenative annulation to prepare fluorene derivative.
通过硫属自由基引发的分子内 1,4-芳基迁移/脱羧级联反应，设计了芳基炔酸酯的氧化三官能化反应，以高产率（高达 98%）制备 1,1-二硫代四取代烯烃。该操作简单的反应在无金属条件下进行，可以进行克级规模的反应，并突出了炔烃的形式 1,1-双官能化。通过双重级联重排来制备高度共轭的四硒化烯烃以及交叉脱氢环化来制备芴衍生物，证明了该方案的合成潜力。
