- Ligand-Controlled Regiodivergence in Nickel-Catalyzed Hydroarylation and Hydroalkenylation of Alkenyl Carboxylic Acids**
-
A nickel-catalyzed regiodivergent hydroarylation and hydroalkenylation of unactivated alkenyl carboxylic acids is reported, whereby the ligand environment around the metal center dictates the regiochemical outcome. Markovnikov hydrofunctionalization products are obtained under mild ligand-free conditions, with up to 99 % yield and >20:1 selectivity. Alternatively, anti-Markovnikov products can be accessed with a novel 4,4-disubstituted Pyrox ligand in excellent yield and >20:1 selectivity. Both electronic and steric effects on the ligand contribute to the high yield and selectivity. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining step induced by the optimal ligand. DFT calculations reveal that in the anti-Markovnikov pathway, repulsion between the ligand and the alkyl group is minimized (by virtue of it being 1° versus 2°) in the rate- and regioselectivity-determining transmetalation transition state.
- Deng, Ruohan,Engle, Keary M.,Fu, Yue,Gao, Yang,Li, Zi-Qi,Liu, Peng,Tran, Van T.
-
supporting information
p. 23306 - 23312
(2020/10/19)
-
- Pyridine-oxazoline and quinoline-oxazoline ligated cobalt complexes: Synthesis, characterization, and 1,3-butadiene polymerization behaviors
-
A series of cobalt complexes supported by pyridine-oxazoline (Pyox) and quinoline-oxazoline (Quox) were synthesized. Determined by single crystal X-ray crystallography, complexes 6a and 7c adopted distorted octahedron and trigonal bipyramid geometries, re
- Guo, Jun,Liu, Heng,Bi, Jifu,Zhang, Chunyu,Zhang, Hexin,Bai, Chenxi,Hu, Yanming,Zhang, Xuequan
-
p. 305 - 312
(2015/08/06)
-
- Efficacious and rapid metal- and solvent-free synthesis of enantiopure oxazolines
-
A rapid and efficient synthesis of oxazolines was performed starting from various nitriles using microwave irradiation combined to metal- and solvent-free conditions to afford high to quantitative yields of the targeted heterocycles.
- Hassani, Rym,Requet, Alexandre,Marque, Sylvain,Gaucher, Anne,Prim, Damien,Kacem, Yakdhane,Hassine, Bchir Ben
-
p. 1275 - 1279
(2015/01/08)
-
- Pd-catalyzed asymmetric aza-Wacker-type cyclization reaction of olefinic tosylamides
-
The Pd-catalyzed asymmetric aza-Wacker-type cyclization reaction of the olefinic tosylamides with molecular oxygen as the green oxidant was developed. Under the optimized conditions, excellent catalytic activity and good enantioselectivity with up to 74%
- Jiang, Feng,Wu, Zhengxing,Zhang, Wanbin
-
scheme or table
p. 5124 - 5126
(2010/11/16)
-
- Palladium(II)-catalyzed enantioselective aerobic dialkoxylation of 2-propenyl phenols: A pronounced effect of copper additives on enantioselectivity
-
A direct O2-coupled Pd(II)-catalyzed enantioselective dialkoxylation of 2-propenylphenols has been developed by utilizing chiral quinoline oxazoline ligands. A detrimental effect of added copper salts on enantioselectivity was observed which is attributed to the displacement of the chiral ligand off of Pd(II). Copyright
- Zhang, Yang,Sigman, Matthew S.
-
p. 3076 - 3077
(2008/04/18)
-
- Steric effects of the ligand in the enantioselective palladium-catalyzed allylic alkylation using chiral oxazolinylpyridines
-
Eight new chiral oxazolinylpyridines were prepared and assessed in the enantioselective palladium-catalyzed allylic substitution of 1,3- diphenylprop-2-enyl acetate with dimethyl malonate. Catalytic activity and enantioselectivity were found to be highly
- Chelucci, Giorgio,Medici, Serenella,Saba, Antonio
-
p. 543 - 550
(2007/10/03)
-
