Copper-catalyzed aerobic asymmetric cross-dehydrogenative coupling of C(sp3)–H bonds driven by visible light,Green Chemistry

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Copper-catalyzed aerobic asymmetric cross-dehydrogenative coupling of C(sp3)–H bonds driven by visible light
Green Chemistry ( IF 9.3 ) Pub Date : 2020-06-19 , DOI: 10.1039/d0gc00262c
Kexu Zhou _{1,

2,

3,

4,

5} , Ying Yu _{1,

2,

3,

4,

5} , Yu-Mei Lin _{1,

2,

3,

4,

5} , Yanjun Li _{1,

2,

3,

4,

5} , Lei Gong _{1,

2,

3,

4,

5}

Affiliation

Asymmetric cross-dehydrogenative coupling (CDC) of C(sp³)–H bonds shows great potential for rapid and stereoselective construction of C–C bonds and use of molecular oxygen as the oxidant for such transformations is appealing in the context of green synthetic methodologies. However, the poor reactivity of oxygen at the ground state and the challenges in controlling the stereochemistry make it extremely difficult to access highly enantioselective aerobic CDC reactions of C(sp³)–H precursors. Herein we report our effort towards this goal via copper-based asymmetric photocatalysis. A chiral-copper catalyst initiates the visible-light-driven oxidative CDC reaction by molecular oxygen, and governs the stereochemistry. In this way, a diastereo- and enantioselective cross-dehydrogenative coupling between carbonyl compounds and xanthene derivatives has been achieved. This work provides an economic and manageable approach to stereoselective C–C bond formation, and demonstrates a potential application of chiral copper catalysts in difficult asymmetric photochemical reactions.

中文翻译：

可见光驱动下的铜催化C（sp3）–H键有氧不对称交叉脱氢偶联

C（sp ³）–H键的不对称交叉脱氢偶联（CDC）显示出快速且立体选择性地构建C–C键的巨大潜力，在绿色合成方法中，使用分子氧作为此类转化的氧化剂非常有吸引力。但是，基态氧的反应性差，控制立体化学的挑战使进入C（sp ³）-H前体的高对映选择性好氧CDC反应极为困难。在这里我们提出我们的努力实现这一目标通过铜基不对称光催化。手性铜催化剂通过分子氧引发可见光驱动的氧化CDC反应，并控制立体化学。以这种方式，已经实现了羰基化合物与x吨衍生物之间的非对映和对映选择性的交叉脱氢偶联。这项工作为立体选择性C–C键的形成提供了一种经济可行的方法，并证明了手性铜催化剂在困难的不对称光化学反应中的潜在应用。

更新日期：2020-07-20

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