Copper-Catalyzed Chemoselective Cyclization Reaction of 2-Isocyanoacetophenone: Synthesis of 4-Hydroxyquinoline Compounds

Qing, Yuan; Rao, Weidong; Wang, Shun‐Yi; Ji, Shun‐Jun

doi:10.1021/acs.joc.9b02903

Cited by 12 publications

(9 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, the notably increased difficulty in the synthesis of electron-rich 5b and the relatively facile synthesis of 5e imply that the reactivity is inversely correlated to the electron density around the isocyanide carbon. Therefore, it is likely the copper catalyst acts more as a Lewis acid, which is in line with recent results reported by us, Zhu, and Ji …”

Section: Resultssupporting

confidence: 90%

“…Therefore, it is likely the copper catalyst acts more as a Lewis acid, which is in line with recent results reported by us, 4c Zhu, 15 and Ji. 16 The synthetic utility of this methodology is underlined by the syntheses of several natural products in a single postinsertion/cyclocondensation reaction. First, we utilized our methodology to couple isocyanobenzoate 1a with ethanolamine (6) to afford the plant alkaloid echinozolinone 17 (7) in 90% yield (Scheme 6a).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Quinazolin-4-ones by Copper-Catalyzed Isocyanide Insertion

et al. 2020

View full text Add to dashboard Cite

Herein, we report a novel copper-catalyzed imidoylative cross-coupling/cyclocondensation reaction between 2-isocyanobenzoates and amines efficiently producing quinazolin-4-ones. The reaction utilizes Cu(II) acetate as an environmentally benign catalyst in combination with a mild base and proceeds well in anisole, a recommended, sustainable solvent. Additionally, the reaction does not require dry conditions or inert atmospheres for optimal performance. The scope of this isocyanide insertion reaction is rather broad, tolerating various functionalized isocyanobenzoates and a range of substituted amines, although the use of aromatic amines as nucleophiles requires microwave heating.

show abstract

Section: Resultssupporting

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Quinazolin-4-ones by Copper-Catalyzed Isocyanide Insertion

et al. 2020

View full text Add to dashboard Cite

show abstract

“…1‐(2‐aminophenyl)‐3‐(4‐methoxyphenyl)propan‐1‐one (3 fg) Yield 234.9 mg 92 % (Catalyst Ru1 ), 229.8 mg 90 % (Catalyst Ru2 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.72 (d, J =8.1 Hz, 1H), 7.24 (t, J =8.4 Hz, 1H), 7.18–7.14 (m, 2H), 6.84 (d, J =8.6 Hz, 2H), 6.84–6.61 (m, 2H), 6.27 (s, 2H), 3.78 (s, 3H), 3.22 (t, J =8.3, 2H), 2.97 (t„ J =7.0 Hz 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 201.84, 158.01, 150.45, 134.35, 133.59, 131.15, 129.41, 117.93, 117.46, 115.89, 114.00, 55.37, 41.35, 29.83.…”

Section: Methodsmentioning

confidence: 99%

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

Maji

Singh

et al. 2020

ChemCatChem

View full text Add to dashboard Cite

A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N‐dimethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N‐diethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N‐dimethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐yl)hydrazineylidene)methyl)‐ aniline and L4=N,N‐diethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half‐sandwich complexes acted as catalysts for C−C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h−1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o‐amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h−1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C−C bond formation has been proposed.

show abstract

“…Isocyanides are important building blocks in modern organic synthesis, which have been widely employed in the construction of various nitrogen-containing compounds because they are easy to handle and exhibit high reactivity. , Given our continuing interest in isocyanide chemistry, herein, we reported a highly efficient and straightforward isocyanide-based formal multicomponent reactions, which provide an atom- and step-economical strategy for preparing bisphosphinoylaminomethane derivatives under mild conditions(Scheme d).…”

Section: Introductionmentioning

confidence: 99%

Direct 1,1-Bisphosphonation of Isocyanides: Atom- and Step-Economical Access to Bisphosphinoylaminomethanes

et al. 2021

Self Cite

View full text Add to dashboard Cite

An atom- and step-economical strategy for the synthesis of bisphosphinoylaminomethanes is reported. This metal-free bisphosphinylation reaction proceeded smoothly through a base-mediated direct 1,1-bisphosphonation of phosphine oxides and isocyanides under mild conditions. The present method offers a facile, efficient, and general approach to a broad range of bisphosphinoylaminomethane derivatives in moderate to good yields.

show abstract

Copper-Catalyzed Chemoselective Cyclization Reaction of 2-Isocyanoacetophenone: Synthesis of 4-Hydroxyquinoline Compounds

Cited by 12 publications

References 26 publications

Synthesis of Quinazolin-4-ones by Copper-Catalyzed Isocyanide Insertion

Synthesis of Quinazolin-4-ones by Copper-Catalyzed Isocyanide Insertion

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

Direct 1,1-Bisphosphonation of Isocyanides: Atom- and Step-Economical Access to Bisphosphinoylaminomethanes

Contact Info

Product

Resources

About