Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St., Cambridge, MA, 02138, USA.
Angew Chem Int Ed Engl. 2020 Jun 8;59(24):9527-9533. doi: 10.1002/anie.201916398. Epub 2020 Apr 1.
Self-sustained Ni cycles are established as a potentially general paradigm in photoredox Ni-catalyzed carbon-heteroatom cross-coupling reactions through a strategy that allows us to recapitulate photoredox-like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable because previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy-transfer-mediated pathways.
通过一种策略，在没有光的情况下，在广泛的底物范围内，在芳基溴的氨化、醚化和酯化反应中，我们能够再现类似于光氧化还原的反应，从而在光氧化还原 Ni 催化中迄今难以捉摸的热 Ni 催化下，建立了 Ni 循环的自维持，这是一种在光氧化还原 Ni 催化中迄今难以捉摸的潜在通用范例。此外，在没有光的情况下进行酯化的可及性尤其值得注意，因为之前在光氧化还原条件下对此转化的机理研究一致地提出了能量转移介导的途径。
