120158-09-0Relevant articles and documents
Controlled Relay Process to Access N-Centered Radicals for Catalyst-free Amidation of Aldehydes under Visible Light
Chang, Sukbok,Jeon, Hyun Ji,Jung, Hoimin,Kim, Dongwook,Lee, Wongyu,Seo, Sangwon
, p. 495 - 508 (2021)
Nitrogen-centered radicals have attracted increasing attention as a versatile reactive intermediate for diverse C–N bond constructions. Despite the significant advances achieved in this realm, the controllable formation of such species under catalyst-free conditions remains highly challenging. Here, we report a new relay process involving the slow in situ generation of a photoactive N-chloro species via C–N bond formation, which subsequently enables mild and selective access to N-centered radicals under visible light conditions. The utility of this approach is demonstrated by the conversion of aldehydes to amides, employing N-chloro-N-sodio carbamates as a practical amidating source. This synthetic operation obviates the need for catalysts, external oxidants, and coupling reagents that are typically required in related processes, consequently allowing high functional group tolerance and excellent applicability for late-stage functionalization. Amides are an important class of structural motifs prevalently found in bioactive compounds and synthetic materials of great significance. Amidation of aldehydes has been established as an atom-efficient strategy for amide synthesis; however, current methods lack in applicability mainly due to the requirement of troublesome reagents. In this article, we describe an unconventional relay process to convert aldehydes to amides under catalyst-, oxidant-, and coupling-reagent-free conditions, which is enabled by the development of a new mechanistic platform that gives efficient and controllable access to N-centered radicals under visible light. A wide range of (hetero)aromatic and aliphatic aldehydes can be employed, including those derived from biologically relevant complex molecules. We anticipate that the accomplished methodological advances, combined with the unique mechanistic features, will lead to the widespread application of the present strategy in broad research fields. A catalyst-free approach for controlled access to N-centered radicals is described, which enables the conversion of aldehydes to amides via an unconventional relay process harnessing visible light. The key tactic relies on the use of photostable N-chloro-N-sodio-carbamate amidating reagent that leads to slow incorporations of a photoactive radical source via C–N formation and other involved intermediates thereafter. This methodology displays excellent applicability and sustainable chemistry credentials and, thus, holds a promise for finding broad applications.
Rh(III)-catalyzed annulation of BOC-protected benzamides with diazo compounds: Approach to isocoumarins
Dong, Guangyu,Li, Chunpu,Liu, Hong
, (2019/04/02)
A mild rhodium-catalyzed annulation of Boc-protected benzamides with diazo compounds via C?C/C?O bond formation has been explored. In the presence of [Cp*RhCl2]2, AgSbF6 and Cs2CO3, Boc-protected benzamides can be effectively annulated to yield isocoumarins in 0.5–2 h.
A New Method for the Synthesis of Amides from Amines: Ruthenium Tetroxide Oxidation of N-Protected Alkylamines
Tanaka, Ken-Ichi,Yoshifuji, Shigeyuki,Nitta, Yoshihiro
, p. 3125 - 3129 (2007/10/02)
A simple synthetic method for the preparation of amides from the corresponding primary alkylamines was elaborated using ruthenium tetroxide (RuO4) oxidation as a key step.
