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Merging Visible Light Photoredox and Gold Catalysis.
Acc Chem Res 2016; 49(10):2261-2272AC

Abstract

Since the beginning of this century, π-Lewis acidic gold complexes have become the catalysts of choice for a wide range of organic reactions, especially those involving nucleophilic addition to carbon-carbon multiple bonds. For the most part, however, the gold catalyst does not change oxidation state during the course of these processes and two-electron redox cycles of the kind implicated in cross-coupling chemistry are not easily accessible. In order to address this limitation and expand the scope of gold catalysis beyond conventional hydrofunctionalization, extensive efforts have been made to develop new oxidative reactions using strong external oxidants capable of overcoming the high potential of the AuI/AuIII redox couple. However, these processes typically require superstoichiometric amounts of the oxidant and proceed under relatively harsh conditions. Moreover, to date, gold-catalyzed oxidative coupling reactions have remained somewhat limited in scope because, for many systems, the desired cross-coupling does not favorably compete with homodimerization or conventional hydrofunctionalization. In 2013, we disclosed a new concept for gold-catalyzed coupling reactions that, rather than involving external oxidants, employs aryl radicals that act as both the oxidant and the coupling partner in overall redox-neutral transformations. For this, we developed a dual catalytic system combining homogeneous gold catalysis with the emerging field of visible light photoredox catalysis. Using aryldiazonium salts, which are known to act as sources of aryl radicals upon activation with reducing photocatalysts, we could achieve intramolecular oxy- and aminoarylations of alkenes upon irradiating the reaction mixtures with visible light. Further studies on this transformation, in which nucleophilic addition onto a gold-activated alkene is followed by C(sp3)-C(sp2) bond formation, expanded the scope of the process to intermolecular, three-component oxyarylation, while inexpensive organic dyes and user-friendly diaryliodonium salts could be employed as alternative photocatalysts and aryl radical sources, respectively. The potential of dual gold/photoredox catalysis was quickly realized by several research groups and a range of diverse new coupling reactions involving nucleophilic addition to π-systems and even P-H and C(sp)-H functionalization have been developed. In addition to the ambient reaction conditions and the simple setup using household light sources or even sunlight, a key advantage of dual gold/photoredox catalysis results from the simultaneous oxidation of gold(I) and coordination of the coupling partner, which results in high levels of selectivity for the cross-coupled products over homodimers. Furthermore, when gold complexes that are not catalytically active prior to oxidation by the aryl radical are employed, background reactions not involving coupling can be suppressed. Notably, this feature has allowed for the successful use of allenes and alkynes, for which conventional hydrofunctionalization pathways are highly favored, opening the door to new transformations involving the most common substrate classes for gold catalysis. In this Account, we provide an overview of dual gold/photoredox catalysis and highlight the potential of this concept to greatly expand the scope of homogeneous gold catalysis and enable the efficient construction of complex organic molecules. Moreover, recent studies on the visible light-promoted synthesis of novel gold(III) complexes suggest that photoredox activation could yet find further applications in gold chemistry beyond coupling.

Authors+Show Affiliations

Organisch-Chemisches Institut, NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster , Corrensstrasse 40, 48149 Münster, Germany.Organisch-Chemisches Institut, NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster , Corrensstrasse 40, 48149 Münster, Germany.Organisch-Chemisches Institut, NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster , Corrensstrasse 40, 48149 Münster, Germany.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

27610939

Citation

Hopkinson, Matthew N., et al. "Merging Visible Light Photoredox and Gold Catalysis." Accounts of Chemical Research, vol. 49, no. 10, 2016, pp. 2261-2272.
Hopkinson MN, Tlahuext-Aca A, Glorius F. Merging Visible Light Photoredox and Gold Catalysis. Acc Chem Res. 2016;49(10):2261-2272.
Hopkinson, M. N., Tlahuext-Aca, A., & Glorius, F. (2016). Merging Visible Light Photoredox and Gold Catalysis. Accounts of Chemical Research, 49(10), pp. 2261-2272.
Hopkinson MN, Tlahuext-Aca A, Glorius F. Merging Visible Light Photoredox and Gold Catalysis. Acc Chem Res. 2016 10 18;49(10):2261-2272. PubMed PMID: 27610939.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Merging Visible Light Photoredox and Gold Catalysis. AU - Hopkinson,Matthew N, AU - Tlahuext-Aca,Adrian, AU - Glorius,Frank, Y1 - 2016/09/09/ PY - 2016/10/19/pubmed PY - 2016/10/19/medline PY - 2016/9/10/entrez SP - 2261 EP - 2272 JF - Accounts of chemical research JO - Acc. Chem. Res. VL - 49 IS - 10 N2 - Since the beginning of this century, π-Lewis acidic gold complexes have become the catalysts of choice for a wide range of organic reactions, especially those involving nucleophilic addition to carbon-carbon multiple bonds. For the most part, however, the gold catalyst does not change oxidation state during the course of these processes and two-electron redox cycles of the kind implicated in cross-coupling chemistry are not easily accessible. In order to address this limitation and expand the scope of gold catalysis beyond conventional hydrofunctionalization, extensive efforts have been made to develop new oxidative reactions using strong external oxidants capable of overcoming the high potential of the AuI/AuIII redox couple. However, these processes typically require superstoichiometric amounts of the oxidant and proceed under relatively harsh conditions. Moreover, to date, gold-catalyzed oxidative coupling reactions have remained somewhat limited in scope because, for many systems, the desired cross-coupling does not favorably compete with homodimerization or conventional hydrofunctionalization. In 2013, we disclosed a new concept for gold-catalyzed coupling reactions that, rather than involving external oxidants, employs aryl radicals that act as both the oxidant and the coupling partner in overall redox-neutral transformations. For this, we developed a dual catalytic system combining homogeneous gold catalysis with the emerging field of visible light photoredox catalysis. Using aryldiazonium salts, which are known to act as sources of aryl radicals upon activation with reducing photocatalysts, we could achieve intramolecular oxy- and aminoarylations of alkenes upon irradiating the reaction mixtures with visible light. Further studies on this transformation, in which nucleophilic addition onto a gold-activated alkene is followed by C(sp3)-C(sp2) bond formation, expanded the scope of the process to intermolecular, three-component oxyarylation, while inexpensive organic dyes and user-friendly diaryliodonium salts could be employed as alternative photocatalysts and aryl radical sources, respectively. The potential of dual gold/photoredox catalysis was quickly realized by several research groups and a range of diverse new coupling reactions involving nucleophilic addition to π-systems and even P-H and C(sp)-H functionalization have been developed. In addition to the ambient reaction conditions and the simple setup using household light sources or even sunlight, a key advantage of dual gold/photoredox catalysis results from the simultaneous oxidation of gold(I) and coordination of the coupling partner, which results in high levels of selectivity for the cross-coupled products over homodimers. Furthermore, when gold complexes that are not catalytically active prior to oxidation by the aryl radical are employed, background reactions not involving coupling can be suppressed. Notably, this feature has allowed for the successful use of allenes and alkynes, for which conventional hydrofunctionalization pathways are highly favored, opening the door to new transformations involving the most common substrate classes for gold catalysis. In this Account, we provide an overview of dual gold/photoredox catalysis and highlight the potential of this concept to greatly expand the scope of homogeneous gold catalysis and enable the efficient construction of complex organic molecules. Moreover, recent studies on the visible light-promoted synthesis of novel gold(III) complexes suggest that photoredox activation could yet find further applications in gold chemistry beyond coupling. SN - 1520-4898 UR - https://www.unboundmedicine.com/medline/citation/27610939/Merging_Visible_Light_Photoredox_and_Gold_Catalysis_ L2 - https://dx.doi.org/10.1021/acs.accounts.6b00351 DB - PRIME DP - Unbound Medicine ER -