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Visible Light Mediated Photoredox Catalytic Arylation Reactions.
Acc Chem Res 2016; 49(8):1566-77AC

Abstract

Introducing aryl- and heteroaryl moieties into molecular scaffolds are often key steps in the syntheses of natural products, drugs, or functional materials. A variety of cross-coupling methods have been well established, mainly using transition metal mediated reactions between prefunctionalized substrates and arenes or C-H arylations with functionalization in only one coupling partner. Although highly developed, one drawback of the established sp2-sp2 arylations is the required transition metal catalyst, often in combination with specific ligands and additives. Therefore, photoredox mediated arylation methods have been developed as alternative over the past decade. We begin our survey with visible light photo-Meerwein arylation reactions, which allow C-H arylation of heteroarenes, enones, alkenes, and alkynes with organic dyes, such as eosin Y, as the photocatalyst. A good number of examples from different groups illustrate the broad application of the reaction in synthetic transformations. While initially only photo-Meerwein arylation-elimination processes were reported, the reaction was later extended to photo-Meerwein arylation-addition reactions giving access to the photoinduced three component synthesis of amides and esters from alkenes, aryl diazonium salts, nitriles or formamides, respectively. Other substrates with redox-active leaving groups have been explored in photocatalyzed arylation reactions, such as diaryliodonium and triarylsulfonium salts, and arylsulfonyl chlorides. We discus some examples with their scope and limitations. The scope of arylation reagents for photoredox reactions was extended to aryl halides. The challenge here is the extremely negative reduction potential of aryl halides in the initial electron transfer step compared to, e.g., aryl diazonium or diaryliodonium salts. In order to reach reduction potentials over -2.0 V vs SCE two consecutive photoinduced electron transfer steps were used. The intermediary formed colored radical anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents.

Authors+Show Affiliations

Institute of Organic Chemistry, University of Regensburg , D-93040 Regensburg, Germany.Institute of Organic Chemistry, University of Regensburg , D-93040 Regensburg, Germany.Institute of Organic Chemistry, University of Regensburg , D-93040 Regensburg, Germany.Institute of Organic Chemistry, University of Regensburg , D-93040 Regensburg, Germany.Institute of Organic Chemistry, University of Regensburg , D-93040 Regensburg, Germany.

Pub Type(s)

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

Language

eng

PubMed ID

27482835

Citation

Ghosh, Indrajit, et al. "Visible Light Mediated Photoredox Catalytic Arylation Reactions." Accounts of Chemical Research, vol. 49, no. 8, 2016, pp. 1566-77.
Ghosh I, Marzo L, Das A, et al. Visible Light Mediated Photoredox Catalytic Arylation Reactions. Acc Chem Res. 2016;49(8):1566-77.
Ghosh, I., Marzo, L., Das, A., Shaikh, R., & König, B. (2016). Visible Light Mediated Photoredox Catalytic Arylation Reactions. Accounts of Chemical Research, 49(8), pp. 1566-77. doi:10.1021/acs.accounts.6b00229.
Ghosh I, et al. Visible Light Mediated Photoredox Catalytic Arylation Reactions. Acc Chem Res. 2016 08 16;49(8):1566-77. PubMed PMID: 27482835.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Visible Light Mediated Photoredox Catalytic Arylation Reactions. AU - Ghosh,Indrajit, AU - Marzo,Leyre, AU - Das,Amrita, AU - Shaikh,Rizwan, AU - König,Burkhard, Y1 - 2016/08/02/ PY - 2016/8/3/entrez PY - 2016/8/3/pubmed PY - 2016/8/3/medline SP - 1566 EP - 77 JF - Accounts of chemical research JO - Acc. Chem. Res. VL - 49 IS - 8 N2 - Introducing aryl- and heteroaryl moieties into molecular scaffolds are often key steps in the syntheses of natural products, drugs, or functional materials. A variety of cross-coupling methods have been well established, mainly using transition metal mediated reactions between prefunctionalized substrates and arenes or C-H arylations with functionalization in only one coupling partner. Although highly developed, one drawback of the established sp2-sp2 arylations is the required transition metal catalyst, often in combination with specific ligands and additives. Therefore, photoredox mediated arylation methods have been developed as alternative over the past decade. We begin our survey with visible light photo-Meerwein arylation reactions, which allow C-H arylation of heteroarenes, enones, alkenes, and alkynes with organic dyes, such as eosin Y, as the photocatalyst. A good number of examples from different groups illustrate the broad application of the reaction in synthetic transformations. While initially only photo-Meerwein arylation-elimination processes were reported, the reaction was later extended to photo-Meerwein arylation-addition reactions giving access to the photoinduced three component synthesis of amides and esters from alkenes, aryl diazonium salts, nitriles or formamides, respectively. Other substrates with redox-active leaving groups have been explored in photocatalyzed arylation reactions, such as diaryliodonium and triarylsulfonium salts, and arylsulfonyl chlorides. We discus some examples with their scope and limitations. The scope of arylation reagents for photoredox reactions was extended to aryl halides. The challenge here is the extremely negative reduction potential of aryl halides in the initial electron transfer step compared to, e.g., aryl diazonium or diaryliodonium salts. In order to reach reduction potentials over -2.0 V vs SCE two consecutive photoinduced electron transfer steps were used. The intermediary formed colored radical anion of the organic dye perylenediimide is excited by a second photon allowing the one electron reduction of acceptor substituted aryl chlorides. The radical anion of the aryl halide fragments under the loss of a halide ion and the aryl radical undergoes C-H arylation with biologically important pyrrole derivatives or adds to a double bond. Rhodamine 6G as an organic photocatalyst allows an even higher degree of control of the reaction. The dye is photoreduced in the presence of an amine donor under irradiation with green light (e.g., 530 nm), yielding its radical anion, which is a mild reducing reagent. The hypsochromic shift of the absorption of the rhodamine 6G radical anion toward blue region of the visible light spectrum allows its selective excitation using blue light (e.g., 455 nm). The excited radical anion is highly reducing and able to activate even bromoanisole for C-H arylation reactions, although only in moderate yield. Photoredox catalytic C-H arylation reactions are valuable alternatives to metal catalyzed reactions. They have an excellent functional group tolerance, could potentially avoid metal containing catalysts, and use visible light as a traceless reagent for the activation of arylating reagents. SN - 1520-4898 UR - https://www.unboundmedicine.com/medline/citation/27482835/Visible_Light_Mediated_Photoredox_Catalytic_Arylation_Reactions_ L2 - https://dx.doi.org/10.1021/acs.accounts.6b00229 DB - PRIME DP - Unbound Medicine ER -