Formal group insertion into aryl C‒N bonds through an aromaticity destruction-reconstruction process

Han, Dandan; He, Qiuqin; Fan, Renhua

doi:10.1038/s41467-018-05637-z

Cited by 15 publications

(7 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Initial tests. In connection with our recent works on the dearomatization conversion of anilines, oxidative dearomatization can transform the aromatic carbon-nitrogen bond in anilines to a carbon-nitrogen double bond by destroying the aromatic system [45][46][47][48][49] . As shown in Fig.…”

Section: Resultsmentioning

confidence: 94%

Conversion of anilines to chiral benzylic amines via formal one-carbon insertion into aromatic C–N bonds

Yang

et al. 2020

Nat Commun

Self Cite

View full text Add to dashboard Cite

Insertion of atoms into aromatic carbon-nitrogen bonds is an appealing method for the synthesis of nitrogen-containing molecules and it has the advantage of the availability and abundance of anilines. However, the direct cleavage of aromatic carbon-nitrogen bonds is challenging due to the particularly inert and stable nature of these bonds. Here we report a formal, enantioselective one-carbon insertion into an aromatic carbon-nitrogen bond via an aromaticity dissembly-reconstruction process to directly convert anilines to chiral α-branched benzylic amines. The process involves oxidative dearomatization of para-substituted anilines, chiral sulfur ylide-mediated asymmetric aziridination, and subsequent rearrangement. Chiral sulfur ylides serve as one-carbon insertion units.

show abstract

Section: Resultsmentioning

confidence: 94%

Conversion of anilines to chiral benzylic amines via formal one-carbon insertion into aromatic C–N bonds

Yang

et al. 2020

Nat Commun

Self Cite

View full text Add to dashboard Cite

show abstract

“…Insertion of TMM group results in formation of spiro intermediate. Now, rearomatization occurs and spiro species is released and trapping of benzylic cation by nucleophilic attack final gives TMM and benzylic methoxylated products [100] …”

Section: Transformations Involving Hypervalent Iodine Reagents and 2 ...mentioning

confidence: 99%

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

View full text Add to dashboard Cite

This review outlines the progress over recent years in the reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium and cobalt. This approach enables organic transformations complimentary to traditional manifolds. Hypervalent iodine reagents play a preeminent role in organic chemistry due to their versatile reactivity, heteroatom ligands and mild reaction conditions. These reagents in combination of transition metal compounds are used in many synthetically useful organic reactions such as oxidation, rearrangement, amination, halogenation, amidation, ring-opening, cyclization and CÀ H and CÀ C functionalization reactions, etc. which are discussed here. Combination with Cobalt 2.3. Reactions of Hypervalent Iodine Reagents with Copper 2.4. Reactions of Hypervalent Iodine Reagents in Combination with Nickel 2.5. Reactions of Hypervalent Iodine Reagents in Combination with Zinc 3. Transformations Involving Hypervalent Iodine Reagents and 2 nd Transition Series Metals 3.1. Reactions of Hypervalent Iodine Reagents in Combination with Ruthenium 3.2. Reactions of Hypervalent Iodine Reagents in Combination With Rhodium 3.3. Reactions of Hypervalent Iodine Reagent in Combination With Palladium 3.4. Reactions of Hypervalent Iodine Reagents in Combination with Silver 4. Transformations Involving Hypervalent Iodine Reagents and 3rd Transition Series Metals 4.1. Reactions of Hypervalent Iodine Reagents in Combination with Rhenium 4.2. Reactions of Hypervalent Iodine Reagents in Combination with Iridium 4.3. Reactions of Hypervalent Iodine Reagents in Combination with Platinum 4.4. Reactions of Hypervalent Iodine Reagents in Combination with Gold 5. Conclusion

show abstract

“…We envisioned that the involved carboxylate (RCO 2 – ) ligand with an electron-withdrawing R group would render the alkene-bound vinyl-Pd(II) species ( A3′ ) cationic because its coordination ability is weaker than that of a halide ligand . According to the classical Dewar–Chatt–Duncanson model, the alkene moiety of A3′ is highly activated so that nucleophilic attack of the released RCO 2 – to invoke the alkene oxypalladation can occur and thus lead to eight-membered palladacycle intermediate C , followed by reductive elimination to furnish the 7- endo -trig hydroacyloxylative cyclization (Scheme c), which would complement the carbocationic 7- endo -trig cyclization promoted by a gold(I) catalyst . On the other hand, the carboxylate (RCO 2 – ) with an electron-donating R group might be indispensable to ensure that its nucleophilicity is strong enough to engage in this putative oxypalladation step.…”

Section: Introductionmentioning

confidence: 99%

Pd(0)-Catalyzed Asymmetric 7-Endo Hydroacyloxylative Cyclization of 1,6-Enyne Enabled by an Anion Ligand-Directed Strategy

Dong

Qian

et al. 2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Despite diversity in reaction mechanisms, the palladium-catalyzed cyclization of 1,6-enyne generally proceeds in a 5exo manner. Herein, we report the development of a Pd(0)-catalyzed hydroacyloxylative cyclization of 1,6-enyne in either 7-endo-trig or 6-exo-trig fashion when paired with an appropriate dihaloacetic acid reactant, such as F 2 HCCO 2 H and Cl 2 HCCO 2 H. Using the combination of Pd 2 (dba) 3 and a chiral phosphine ligand, the hydroacyloxylative cyclization of 1,6-enyne bearing a 1,1-disubstituted alkene moiety readily gives highly enantiopure seven-membered heterocycles while the reaction of those having a 1,2-disubstituted alkene affords six-membered rings with moderate enantioselectivity. Preliminary experimental studies suggest a reaction mechanism featuring an unusual E-to-Z vinyl-Pd(II) isomerization and alkene trans-oxypalladation, which is proven to be governed by the rationally selected carboxylate.

show abstract

Formal group insertion into aryl C‒N bonds through an aromaticity destruction-reconstruction process

Cited by 15 publications

References 70 publications

Conversion of anilines to chiral benzylic amines via formal one-carbon insertion into aromatic C–N bonds

Conversion of anilines to chiral benzylic amines via formal one-carbon insertion into aromatic C–N bonds

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

Pd(0)-Catalyzed Asymmetric 7-Endo Hydroacyloxylative Cyclization of 1,6-Enyne Enabled by an Anion Ligand-Directed Strategy

Contact Info

Product

Resources

About