85553-43-1Relevant articles and documents
Transition-Metal-Free Synthesis of Heterobiaryls through 1,2-Migration of Boronate Complex
Paul, Swagata,Das, Kanak Kanti,Manna, Samir,Panda, Santanu
supporting information, p. 1922 - 1927 (2020/02/04)
The synthesis of a diverse range of heterobiaryls has been achieved by a transition-metal-free sp2–sp2 cross-coupling strategy using lithiated heterocycle, aryl or heteroaryl boronic ester and an electrophilic halogen source. The construction of heterobiaryls was carried out through electrophilic activation of the aryl–heteroaryl boronate complex, which triggered 1,2-migration from boron to the carbon atom. Subsequent oxidation of the intermediate boronic ester afforded heterobiaryls in good yield. A comprehensive 11B NMR study has been conducted to support the mechanism. The cross coupling between two nucleophilic cross coupling partners without transition metals reveals a reliable manifold to procure heterobiaryls in good yields. Various heterocycles like furan, thiophene, benzofuran, benzothiophene, and indole are well tolerated. Finally, we have successfully demonstrated the gram scale synthesis of the intermediates for an anticancer drug and OLED material using our methodology.
Metal-Free Aerobic Oxidative Selective C-C Bond Cleavage in Heteroaryl-Containing Primary and Secondary Alcohols
Xia, Anjie,Qi, Xueyu,Mao, Xin,Wu, Xiaoai,Yang, Xin,Zhang, Rong,Xiang, Zhiyu,Lian, Zhong,Chen, Yingchun,Yang, Shengyong
, (2019/05/07)
A transition-metal-free aerobic oxidative selective C-C bond-cleavage reaction in primary and secondary heteroaryl alcohols is reported. This reaction was highly efficient and tolerated various heteroaryl alcohols, generating a carboxylic acid derivative and a neutral heteroaromatic compound. Experimental studies combined with density functional theory calculations revealed the mechanism underlying the selective C-C bond cleavage. This strategy also provides an alternative simple approach to carboxylation reaction.
Non-Directed Cross-Dehydrogenative (Hetero)arylation of Allylic C(sp3)?H bonds enabled by C?H Activation
Lerchen, Andreas,Knecht, Tobias,Koy, Maximilian,Ernst, Johannes B.,Bergander, Klaus,Daniliuc, Constantin G.,Glorius, Frank
supporting information, p. 15248 - 15252 (2018/10/20)
Herein, we report the selective, non-directed and cross-dehydrogenative coupling of allylic C(sp3)?H bonds with C(sp2)?H bonds of (hetero)arenes. The methodology employs olefins and (hetero)arenes which are abundantly available chemical feedstocks, and could be applied in late-stage functionalization reactions of pharmaceuticals. Furthermore, the system exclusively delivers the allylic C?C coupling products highlighting the preservation of the olefin substitution pattern for further derivatization.