Generation of Ben3yres Using TMP-Zincate

我们开发了以R_2Zn(TMP)Li为关键反应，通过去质子锌化反应制备功能化苯的新方法，并描述了配体对苯形成的显著影响。用Me_2Zn(TMP)Li对各种间取代的溴苯进行脱质子镀锌，可以一锅生成各种3官能团苯，特别是那些具有亲电取代基的苯，如酯、酰胺和氰基。另一方面，用^tBu_2Zn(TMP)Li/ /进行镀锌，然后用I_2进行亲电俘获，证明了制备1,2,3-三取代芳香族化合物的有力工具。所得的1,2,3-三取代苯可作为Me_3ZnLi卤素-锌交换反应生成3-取代苯的前体。这些方法对功能化不对称苯的合成具有较好的通用性，在各种天然产物和功能材料的新合成中具有一定的应用价值。此外，这些结果强调了在酸盐配合物的中心金属上的旁观者配体在新的酸盐配合物促进反应的发展中作为可调功能的效用。

We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R_2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various m-substituted bromobenzenes using Me_2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particulary those with electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with ^tBu_2Zn(TMP)Li/ followed by electrophilic trapping (with I_2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds. The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions using Me_3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions.