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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Alkoxy- and amidocarbonylation of functionalised aryl and heteroaryl halides catalysed by a Bedford palladacycle and dppf: a comparison with the primary Pd(II) precursors (PhCN)(2)PdCl2 and Pd(OAc)(2)
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Alkoxy- and amidocarbonylation of functionalised aryl and heteroaryl halides catalysed by a Bedford palladacycle and dppf: a comparison with the primary Pd(II) precursors (PhCN)(2)PdCl2 and Pd(OAc)(2)

机译:Bedford palladacycle和dppf催化的官能化芳基和杂芳基卤化物的烷氧基和酰胺羰基化:与主要Pd(II)前体(PhCN)(2)PdCl2和Pd(OAc)(2)的比较

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摘要

The versatility of a Bedford-type palladacycle 1, namely [{Pd(mu-Cl){kappa(2)-P,C-P(OC6H2-2,4-Bu-t(2))-(OC6H3-2,4-tBu(2))(2)}}(2)], as a primary Pd source, in combination with the ligand bis-1, 1'-(diphenylphosphino)ferrocene (dppf) has been established in carbonylation reactions of aryl and heteroaryl bromides with methanol, piperidine and related nucleophiles. Palladacycle 1 has been compared with other primary Pd sources, e.g. (PhCN)(2)PdCl2 and Pd(OAc)(2). The efficacy of the carbonylation processes appear to be linked to the [Pd] concentration, substrate : catalyst ratio, CO pressure and reaction temperature. In amidocarbonylation, double carbonylation is observed for certain organohalides. In the case of 2,5-dibromopyridine, regioselective amination (Hartwig-Buchwald type) also occurs as a side-reaction.
机译:贝德福德型Palladacycle 1的多功能性,即[{Pd(mu-Cl){kappa(2)-P,CP(OC6H2-2,4-Bu-t(2))-(OC6H3-2,4- tBu(2))(2)}}(2)]作为主要的Pd源,已与配体bis-1结合,在芳基和杂芳基的羰基化反应中建立了1'-(二苯基膦基)二茂铁(dppf)溴化物与甲醇,哌啶和相关亲核试剂。已将Palladacycle 1与其他主要Pd来源(例如(PhCN)(2)PdCl2和Pd(OAc)(2)。羰基化过程的功效似乎与[Pd]浓度,底物:催化剂比例,CO压力和反应温度有关。在酰胺羰基化中,某些有机卤化物会发生双羰基化。在2,5-二溴吡啶的情况下,区域选择性胺化(Hartwig-Buchwald型)也作为副反应发生。

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