Bifunctional Copper-Based Photocatalyst for Reductive Pinacol-Type Couplings
Bifunctional Copper-Based Photocatalyst for Reductive Pinacol-Type Couplings
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DOI：
10.1021/acscatal.9b01718
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发表时间：
2019-10-01
期刊：
影响因子：
12.9
通讯作者：
Collins, Shawn K.
中科院分区：
文献类型：
--
作者：
Caron, Antoine;Morin, Emilie;Collins, Shawn K.
一种双功能铜基光催化剂已经制备，采用吡唑-吡啶配体掺入磺酰胺部分，作为分子内氢键供体的光化学PCET过程中的功能。在典型的还原PCET过程中，光催化剂和H-键供体必须分别具有适当的氧化还原电位和pK（α），以促进PCET。当在双功能催化剂如Cu（pypzs）（BINAP）-BF 4中协同工作时，H-键供体的pK（a）可以具有小几个数量级的酸度，并且仍然有效地促进PCET过程。可以使用贱金属衍生的光催化剂进行还原频哪醇型偶联，以从容易获得的醛和酮得到有价值的二醇（24个实施例，46-99%产率）。
A bifunctional copper-based photocatalyst has been prepared that employs a pyrazole-pyridine ligand incorporating a sulfonamide moiety that functions as an intramolecular hydrogen-bond donor for a photochemical PCET process. In typical reductive PCET processes, the photocatalyst and H-bond donor must have an appropriate redox potential and pK(a), respectively, to promote the PCET. When working in concert in a bifunctional catalyst such as Cu(pypzs)(BINAP)-BF4, the pK(a) of the H-bond donor can have an acidity that is orders of magnitude less and still efficiently promote the PCET process. A reductive pinacol-type coupling can be performed using a base-metal derived photocatalyst to afford valuable diols (24 examples, 46-99% yield), from readily available aldehydes and ketones.