We developed a regiodivergent syntheses of 4- and 5-bromo-substituted 1,2,3-triazoles in copper-catalyzed azide–alkyne cycloadditions (CuAACs) by taking advantage of bromo(phosphoryl)ethyne 1 as a bromoethyne equivalent. A one-shot dephosphorylative CuAAC of 1 afforded 4-bromotriazoles, which was transformed into a histone deacetylase 8 (HDAC8)-selective inhibitor, NCC-149. However, the direct CuAAC catalyzed by CuI/Cu(OAc)₂ provided 5-bromo-4-phosphoryltriazoles. The consecutive nucleophilic substitution of the bromo group with thiols followed by MeOK-promoted dephosphorylation gave 5-thio-substituted triazoles.

中文翻译：

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过程控制的区域发散性铜催化的叠氮化物-炔烃环加成反应：量身定制的由溴（磷酰基）乙炔合成的4-和5-溴三唑。

我们通过利用溴（磷酰基）乙炔1作为溴乙炔当量的优势，在铜催化的叠氮化物-炔烃环加成反应（CuAAC）中开发了4-和5-溴取代的1,2,3-三唑的区域发散性合成。一次性脱磷酸化CuAAC为1可得到4-溴三唑，将其转化为组蛋白脱乙酰基酶8（HDAC8）选择性抑制剂NCC-149。然而，由CuI / Cu（OAc）₂催化的直接CuAAC提供了5-溴-4-磷酰基三唑。溴基团被硫醇连续亲核取代，然后由MeOK促进的去磷酸化，得到5-硫基取代的三唑。