A dearomative 1,4-hydroamination of nonactivated arenes has been developed, using a key arene–arenophile photocycloaddition strategy to disrupt aromaticity. Palladium catalysis with K-Selectride® as ...a hydride source uniquely enables selective reactivity and provides access to a range of substituted 1,4-cyclohexadienes from aromatic starting materials. We demonstrate a few synthetic applications of this scalable procedure by preparing highly-functionalized small molecules in three to four steps from naphthalene.
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Playing Reversi with H and N: A copper‐catalyzed intermolecular regioselective hydroamination of styrenes with polymethylhydrosiloxane and hydroxylamine derivatives has been developed. The catalysis ...accommodates challenging β‐substituted substrates. Moreover, the chiral biphosphine‐ligated copper complex successfully forms benzylamines with good enantiomeric ratios.
The direct modification of structurally complex natural product dehydroepiandrosterone (DHEA) through Iron-catalyzed direct hydroamination of DHEA with various nitro(hetero)arenes was carried out to ...afford 5α-arylamino-DHEAs (1–25) in good yields (53–72%). Though as a radical reaction, it features high stereoselectivity, and only the 5α-substituted derivatives were produced. The in vitro antiproliferative activity of these synthesized compounds against the human breast cancer MCF-7 cell was evaluated, showing that most of DHEA analogues possessed the moderate cytotoxic activity. The preliminary structure-activity relationship analysis revealed that the electron-withdrawing groups installed at the para-position of arylamine ring had a great contribution to the improvement of the DHEA’s cytotoxic potency. Among them, (4-trifluoromethylaniline)-DHEA (4) displayed the most potent cytotoxicity, with an IC50 value of 19.3 μM, which was 2.3-fold more active than DHEA.
The front cover picture, designed by L. Duarte de Almeida et al. illustrates the successful application of a well‐defined manganese PNP pincer complex in the formal hydroamination of allylic alcohols ...with primary and secondary amines as well as with N‐heterocycles. The corresponding γ‐amino alcohols were obtained in up to 94% yield in a tandem reaction combining dehydrogenation/Michael addition/hydrogenation sequence. The properties of these non‐innocent pincer ligands allowed application of this non‐noble metal catalyst in organic synthesis with a broad substrate scope. Details can be found in the communication by M. Beller, K. Junge and co‐workers (L. Duarte de Almeida, F. Bourriquen, K. Junge, M. Beller, Adv. Synth. Catal. 2021, 363, 4177–4181; DOI: 10.1002/adsc.202100081).
•Stepwise post-synthetic modification of surface nitrogen-enriched Cu(BDCNH2) metal-organic frameworks (MOFs).•preparation of Cu(BDCNH2) -AuNTf2.•Various techniques, including FT-IR, XRD, SEM, BET, ...EDS, ICP, and TGA, characterized.•This method was performed efficiently under mild conditions and provided a general and convenient route for synthesizing allylamino E-enamides with good yield and high stereoselectivity.
Here, we prepared an efficient and reusable catalyst by stepwise post-synthetic modification of surface nitrogen-enriched Cu(BDCNH2) metal-organic frameworks (MOFs) and used it as a catalyst for the preparation of Cu(BDCNH2) -AuNTf2. Catalytic performance results of the Cu(BDCNH2)-AuNTf2 catalyst showed high efficiency in modulating the microenvironment of AuNTf2 Nanoparticles. Successful preparation of Cu(BDCNH2)-AuNTf2 catalyst has been proven by various techniques, including FT-IR, XRD, SEM, BET, EDS, ICP, and TGA. The synthesis of allylamino E-enamides with good yield and high stereoselectivity was carried out under mild conditions in the presence of AuNTf2 Nanoparticle catalysis. Clean method, easy catalyst manufacturing, high efficiency, and recyclability are the most important advantages of this procedure.
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Systematic reaction path exploration revealed the entire mechanism of Knowles’ light‐promoted catalytic intramolecular hydroamination via radical processes. In their Research Article (e202211936), Yu ...Harabuchi, Satoshi Maeda, and co‐workers investigated the energetically favorable reaction path by constructing reaction path networks and searching for the seam of crossing geometries. Calculations showed that the reduction and proton shuttle process proceeded concertedly.
A system comprising TiCl
4 and
t-BuNH
2 converts alkynes and hydrazines directly to the corresponding indoles in a highly regioselective manner and generates substituted pyrroles from a 1,3-diyne and ...aniline derivatives.
A system comprising TiCl
4 and
t-BuNH
2 acts as a catalyst for highly regioselective hydroamination reactions of alkynes using hydrazines and at the same time a Lewis acid in the transformation of the generated hydrazones into indole derivatives, while a 1,3-diyne is converted to pyrroles using the same precatalyst.
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Hydroamination, an atom-economic one-step reaction that refers to the addition of an NH unit into CC/CX multiple bonds, provides an ideally efficient methodology to construct C–N ...bonds. Due to the presence of the f-orbitals, organo- lanthanides and actinides mediated hydroamination generally reveal distinct differences and in some cases complementary catalytic behaviors when compared to early/late-transition metals and main group metal complexes. The earliest organo-f-metal catalyzed hydroamination can be dated back to 1989, and since then numerous organo-f-metal complexes have been designed and systematically explored. According to the types of the ligands, the authors roughly divided the past thirty-three years of development into three stages. In the 1st stage (1989–1998), only metallocene-types, lanthanocenes and actinocenes, served as the catalysts. In the 2nd stage (1999–2008), post-metallocene complexes appeared and started to grow thereafter, and in a ten-year development, the number of reports on both metallocene and post-metallocene catalysts is similar. These two stages have been comprehensively reviewed previously. Since 2009 (3rd stage), more and more post-metallocene catalysts were exploited and soon became the predominant type of catalysts. Therefore, this review covers the reports in the 3rd stage, which mainly are post-metallocene complexes that bear mono-, bi-, tri-, and tetra-dentate ligands. Different from previous reviews that only focus on challenging alkene or alkyne substrates (CC multiple bonds), this review also includes CX multiple bonds containing substrates to give a better catalytic hydroamination map of the organo-f-metal complexes. In the end, we also give our personal “Quo Vadis” opinions on some challenging questions and where this field should continue to develop.
The Sonogashira reaction first, and then intra-molecular hydroamination of alkyne catalyzed by CuI/o-phen was proved to be an efficient method for the synthesis of imidazo2,1-aisoquinoline, ...phenanthro9′,10′:4,5imidazo2,1-aisoquinoline and acenaphtho1′,2′:4,5imidazo 2,1-aisoquinoline derivatives in the presence of Cs2CO3.
The Sonogashira reaction first, and then intra-molecular hydroamination of alkyne catalyzed by CuI/o-phen was proved to be an efficient method for the synthesis of imidazo2,1-aisoquinoline derivatives in the presence of Cs2CO3. Display omitted
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