437709-29-0Relevant academic research and scientific papers
The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)-O Arylation
Mills, L. Reginald,Monteith, John J.,Dos Passos Gomes, Gabriel,Aspuru-Guzik, Alán,Rousseaux, Sophie A. L.
supporting information, p. 13246 - 13254 (2020/09/01)
The ability to understand and predict reactivity is essential for the development of new reactions. In the context of Ni-catalyzed C(sp3)-O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp3)-O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.
Systematic repression of β-silyl carboeation stabilization
Creary, Xavier,Kochly, Elizabeth D.
experimental part, p. 2134 - 2144 (2009/08/07)
Solvolysis of 1-(trimethylsilylmethyl)cyclopropyl mesylate in CD 3CO2D gives ring-opened products as well as methylenecyclopropane. The rate enhancement due to the β-trimethylsilyl group is a factor of about 106. The large
