Hu Chenyang, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202208921. doi: 10.1002/anie.202208921. Epub 2022 Aug 18.
We describe the synthesis of a cyapho(dicyano)methanide salt, [K(18-crown-6)][C(CN) (CP)], from reaction of [Na(18-crown-6)][PH ] (18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane) with 1,1-diethoxy-2,2-dicyanoethylene (EtO) C=C(CN) . The reaction proceeds through a Michael addition-elimination pathway to afford [Na(18-crown-6)][HP{C(OEt)=C(CN) }]. Addition of a strong, non-nucleophilic base (KHMDS) to this intermediate results in the formation of [K(18-crown-6)][C(CN) (CP)]. Subsequent reactivity studies reveal that the cyapho(dicyano)methanide ion is susceptible to protonation with strong acids to afford the parent acid HC(CN) (CP). The reactivity of the cyaphide moiety in [C(CN) (CP)] was explored through coordination to metal centers and in cycloaddition reactions with azides.
我们描述了一种氰基（二氰基）甲烷盐[K(18-冠-6)][C(CN)(CP)]的合成，该盐由[Na(18-冠-6)][PH]（18-冠-6 = 1,4,7,10,13,16-六氧杂环十八烷）与1,1-二乙氧基-2,2-二氰基乙烯(EtO)C=C(CN)反应制得。反应通过迈克尔加成-消除途径进行，得到[Na(18-冠-6)][HP{C(OEt)=C(CN)}]。向该中间体中加入一种强的非亲核碱（KHMDS）会导致[K(18-冠-6)][C(CN)(CP)]的形成。随后的反应性研究表明，氰基（二氰基）甲烷离子易被强酸质子化，生成母体酸HC(CN)(CP)。通过与金属中心配位以及与叠氮化物的环加成反应，探索了[C(CN)(CP)]中氰基部分的反应性。
