摘要：

Off and on: A nickel‐catalyzed benzannulation of alkynylboronates provides functionalized phenols with high levels of chemo‐ and regioselectively. While transmetalation of organoboron intermediate to organonickel does not occur during cycloaddition, it is "switched on" by addition of base, thus allowing a one‐pot benzannulation and cross‐coupling to be realized (see scheme; Pin=pinacolato, Ms=mesyl). <img class="figure__image" src="https://wol-prod-cdn.literatumonline.com/cms/attachment/87347f15-c39a-4162-a78e-fb69eee952a5/mcontent.gif" data-lg-src="https://wol-prod-cdn.literatumonline.com/cms/attachment/27b94328-22d0-4fee-8717-f3da6f54878c/mcontent.jpg">

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