A powerful approach to alkoxy radical-mediated remote C(sp3)-H bonds functionalization
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摘要:
The activation of inert C(sp3)-H bonds with control of reactivity and selectivity is one of the central topics in chemical sciences.In this context,alkoxy radical-mediated 1,5-hydrogen atom transfer allows the regioselective transformation of inert C(sp3)-H bonds to access functionalized molecules which would otherwise be inaccessible.Although some preliminary but elegant results have been disclosed,this chemistry remains challenging and largely underexploited for the following reasons:(1) the bond dissociation energy of O-H bonds is quite high (105 kcal/mol),and therefore the direct formation of alkoxy radicals from alcohols is truly difficult;and (2) the transient alkoxy radicals are too reactive to harness in many cases.Accordingly,various prefunctionalized precursors (e.g.,peroxy compounds,nitrite esters,hypohalites,N-alkoxylpyridine-2-thiones,N-alkoxyphthalimides,etc.) are usually employed to generate alkoxy radicals.Despite advances,the development of catalytic approaches for the straightforward conversion of alcohols to alkoxy radicals under mild and environmentally friendly are highly desirable [1].