Photoredox activation for the direct β-arylation of ketones and aldehydes.

Photoredox activation for the direct β-arylation of ketones and aldehydes.
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DOI:
10.1126/science.1232993
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发表时间:
2013-03-29
期刊:
Science (New York, N.Y.)
影响因子:
--
通讯作者:
MacMillan DW
MacMillan DW
中科院分区:
其他
文献类型:
--
作者:
Pirnot MT;Rankic DA;Martin DB;MacMillan DW

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饱和醛和酮的直接β-活化长期以来一直是一个难以捉摸的转变。我们发现,光氧化还原催化与有机催化相结合可以导致从酮和醛中瞬时产生5π电子β-烯胺基自由基,这些自由基与羰基β-位上的氰基取代的芳基环快速偶联。这种活化模式适用于广泛的羰基β-官能化反应,并且适合于对映选择性催化。
The direct β-activation of saturated aldehydes and ketones has long been an elusive transformation. We found that photoredox catalysis in combination with organocatalysis can lead to the transient generation of 5π-electron β-enaminyl radicals from ketones and aldehydes that rapidly couple with cyano-substituted aryl rings at the carbonyl β-position. This mode of activation is suitable for a broad range of carbonyl β-functionalization reactions and is amenable to enantioselective catalysis.
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