1192-28-5Relevant articles and documents
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Fox,Dunn,Stoddard
, p. 410,411 (1941)
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Minisci-Type C–H Cyanoalkylation of Heteroarenes Through N–O/C–C Bonds Cleavage
Jian, Yong,Chen, Ming,Yang, Chao,Xia, Wu-jiong
, p. 1439 - 1442 (2020)
A visible-light-induced C–H cyanoalkylation of heteroarenes was described, in which cycloketone oximes were readily transformed into carbon-centered radicals with a terminal cyano-group via N–O/C–C bonds cleavage in one phtochemical step. This reaction protocol displayed a broad substrate scope of heterocycle compounds, and it provided a promising strategy for the installation of cyanoalkyl groups onto heteroarenes.
Nickel-Catalyzed NO Group Transfer Coupled with NOxConversion
Padmanaban, Sudakar,Choi, Jonghoon,Vazquez-Lima, Hugo,Ko, Donghwi,Yoo, Dagyum,Gwak, Jinseong,Cho, Kyung-Bin,Lee, Yunho
supporting information, p. 4585 - 4593 (2022/03/02)
Nitrogen oxide (NOx) conversion is an important process for balancing the global nitrogen cycle. Distinct from the biological NOx transformation, we have devised a synthetic approach to this issue by utilizing a bifunctional metal catalyst for producing value-added products from NOx. Here, we present a novel catalysis based on a Ni pincer system, effectively converting Ni-NOx to Ni-NO via deoxygenation with CO(g). This is followed by transfer of the in situ generated nitroso group to organic substrates, which favorably occurs at the flattened Ni(I)-NO site via its nucleophilic reaction. Successful catalytic production of oximes from benzyl halides using NaNO2 is presented with a turnover number of >200 under mild conditions. In a key step of the catalysis, a nickel(I)-?NO species effectively activates alkyl halides, which is carefully evaluated by both experimental and theoretical methods. Our nickel catalyst effectively fulfills a dual purpose, namely, deoxygenating NOx anions and catalyzing C-N coupling.
A modular, low footprint and scalable flow platform for the expedient α-aminohydroxylation of enolizable ketones
Kassin, Victor-Emmanuel H.,Morodo, Romain,Toupy, Thomas,Jacquemin, Isaline,Van Hecke, Kristof,Robiette, Rapha?l,Monbaliu, Jean-Christophe M.
supporting information, p. 2336 - 2351 (2021/04/07)
The unique reactivity profile of α-chloronitroso derivatives is expressed to its fullest potential through the development of an integrated, modular and scalable continuous flow process for the electrophilic α-aminohydroxylation of various enolizable ketones. Flow conditions contribute to mitigating the high reactivity and toxicity of α-chloronitroso derivatives and provide an efficient, versatile and safe protocol for the α-aminohydroxylation of ketones with a minimal footprint. Fundamental aspects of the α-aminohydroxylation process were computed by DFT and further supported the experimental observations, hence leading to the unprecedented α-chloronitroso-based α-aminohydroxylation of primary, secondary and tertiary substrates. Recycling of the carbon backbone of the α-chloronitroso derivatives provides a high atom economy for the preparation of value-added molecules. This work showcases α-chloronitroso derivatives as economic and efficient vehicles for transferring electrophilic synthons of hydroxylamine toward nucleophilic enolates. A representative range of precursors and analogs of pharmaceutical active ingredients, including WHO essentials and drugs in shortage (such as epinephrine and ketamine), are prepared within minutes according to a fully concatenated process. The process features sequential modules with distinct unit operations including chemical transformations and multiple in-line extractions. The process relies on an upstream chemical Generator that manages the preparation of α-chloronitroso derivatives and that feeds downstream a series of α-aminohydroxylation modules. The setup is amenable to the addition of libraries of compounds for feeding upstream the process of discovery in medicinal chemistry and is transposable to pilot scale. Several layers of in-line analytical procedures are featured to improve process control and safety.
