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Rings aplenty: A HOTf‐catalyzed (Tf=trifluoromethanesulfonyl) Povarov reaction of alkenyldiazo species has been developed and delivers diazo‐containing cycloadducts stereoselectively (see scheme). The resulting cycloadducts provide access to six‐ and seven‐membered azacycles through the generation of metal carbenes as well as the functionalization of diazo group.
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