Merging C–C σ-bond activation of cyclobutanones with CO₂ fixation via Ni-catalysis

Abstract

A carboxylative Ni-catalyzed tandem C-C σ-bond activation of cyclobutanones followed by CO2-electrophilic trapping is documented as a direct route to synthetically valuable 3-indanone-1-acetic acids. The protocol shows an adequate functional...

Palladium- and nickel-catalyzed cascade enantioselective ring-opening/coupling reactions of cyclobutanones

“…42 Recently, Bertuzzi and Bandini reported a Ni-catalyzed C–C bond activation of cyclobutanones followed by CO 2 -electrophilic trapping to provide 3-indanone-1-acetic acids (Scheme 18). 43 The precatalyst [Ni( L10 )Cl 2 ] prepared from ( R , R )- L10 and Ni(dme)Cl 2 was employed as the catalyst. Although enantiopure ligands were employed, the stereochemistry outcome of the products was not mentioned.…”

Graphene‐Oxide Mediated Chemodivergent Ring‐Opening of Cyclobutanols

“…Our group has recently embraced the fascinating and challenging profile of C—C σ‐bond activation modes for the generation of chemical diversity. [ 4‐5 ] In particular, the ring‐opening of strained C4‐cyclic scaffolds ( i.e ., cyclobutanones, cyclobutanols) has emerged as one of the most powerful strategies to build‐up complex organic molecular architectures starting from readily available small organic compounds. [ 6 ]…”

An Improved Synthesis of Chiral 2,2′-Bipyridine Ligand C3-ACBP Without Column Chromatography

“…All solvents except DMF and THF which were treated prior with 4Å molecular sieve were used without further purification. 1 H NMR and 13 C NMR spectra were recorded at room temperature in CDCl3 on 400 MHz instrument with tetramethylsilane (TMS) as internal standard. Optical rotations were measured by polarimeter.…”

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.82 (dd, J = 4.6, 1.7 Hz, 1 H), 6.99 (dd, J = 8.2, 4.6 Hz, 1 H), 6.87 (dd, J = 8.3, 1.8 Hz, 1 H), 4.81-4.73 (m, 1 H), 2.12 (dd, J = 7.6, 5.4 Hz, 1 H), 1.41 (d, J = 6.3 Hz, 3 H). 13 To a stirred solution of 3,3′-(2S,4S)-pentane-2,4-diylbis(oxy)bis(2-iodopyridine) [(S,S)-3; 25.51 g, 50 mmol] in DMF (200 mL) was added activated Cu powder (31.77 g, 500 mmol) under N 2 atmosphere. The mixture was heated at 160 °C for 14 h. After completion of the reaction as indicated by TLC, the reaction mixture was cooled to rt.…”

“…3b The chiral 2,2′-bipyridine ligands with central, [3][4][5][6][7] planar, 8 or axial chirality 9,10 have been synthesized and applied for a variety of reactions, and some of them perform excellently. Among them, an axially chiral 2,2′-bipyridine ligand C3-ACBP has been developed and used in asymmetric C-H functionalization, 10 O-H insertion, 10a arylation of N-tosylarylimines, 11 desymmetric C-O coupling, 12 diastereoselective C-C activation, 13 and so on; [14][15][16] and promising results have been achieved. Due to the relatively simple synthetic process of the C3-ACBP ligand and its encouraging performance in several types of reactions, we speculate that its applications in asymmetric catalysis will be extended, and its required amount will increase in the future.…”