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New symmetric and unsymmetric B,N,B‐doped benzo[4]helicenes 3–6 a/b have been achieved in good yields, using a three‐step process, starting from N(tolyl)3 in a highly divergent manner (7 examples). A borinic acid functionalized 1,4‐B,N‐anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo‐substituted B,N,B‐benzo[4]helicenes...
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