The Experts below are selected from a list of 300 Experts worldwide ranked by ideXlab platform

Hyeung-geun Park - One of the best experts on this subject based on the ideXlab platform.

Byeong-seon Jeong - One of the best experts on this subject based on the ideXlab platform.

Yo-han Park - One of the best experts on this subject based on the ideXlab platform.

Robert R. Knowles - One of the best experts on this subject based on the ideXlab platform.

  • Catalytic Alkylation of remote c h bonds enabled by proton coupled electron transfer
    Nature, 2016
    Co-Authors: Gilbert J. Choi, David C. Miller, Carol J. Gu, Robert R. Knowles
    Abstract:

    Catalytic Alkylation of C–H bonds is achieved via homolysis of N–H bonds of N-alkyl amides through proton-coupled electron transfer. In two separate reports, Robert Knowles and colleagues, and John Chu and Tomislav Rovis report the selective homolysis of selected amidyl N–H bonds through a photoCatalytic proton-coupled electron-transfer process. The resulting radical enables C–H abstraction and radical Alkylation at the unactivated 5 position on the aliphatic chain of the N-alkyl amide. As this method does not rely on pre-activation of the amidyl N–H bond or the use of haloamides, it offers a potentially simpler solution than previous approaches to radical amidyls. Additionally, the subsequent 1,5-hydrogen-atom transfer offers a route to selective C–C bond formation in the presence of alkyl amides. Despite advances in hydrogen atom transfer (HAT) catalysis1,2,3,4,5, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen–hydrogen (N–H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination6,7,8,9,10,11 and directed carbon–hydrogen (C–H) bond functionalization12,13,14,15,16. In the latter process—a subset of the classical Hofmann–Loffler–Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C–H bonds17,18,19,20,21. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon–carbon (C–C) bonds. Here we report an approach that overcomes these limitations by homolysing the N–H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C–H abstraction and radical Alkylation steps. This C–H Alkylation represents a Catalytic variant of the Hofmann–Loffler–Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C–C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

  • Catalytic Alkylation of remote C–H bonds enabled by proton-coupled electron transfer
    Nature, 2016
    Co-Authors: Gilbert J. Choi, David C. Miller, Carol J. Gu, Robert R. Knowles
    Abstract:

    Catalytic Alkylation of C–H bonds is achieved via homolysis of N–H bonds of N-alkyl amides through proton-coupled electron transfer.

Jin-mo Ku - One of the best experts on this subject based on the ideXlab platform.