Metal cation-exchanged montmorillonite (Mn+-mont)-catalysed aromatic alkylation with aldehydes and ketones

Aryl Cations from Aromatic Halides. Photogeneration and Reactivity of 4-Hydroxy(methoxy)phenyl Cation

“…After 24 h of irradiation, purification (cyclohexane/ ethyl acetate 9:1 as the eluant) of the raw photolisate afforded 42 mg of 3 (30% yield) and mixtures containing 24 mg of 17 (8% yield), 24.5 mg of 1-(1-(p-hydroxyphenyl)-1-(2,2,2-trifluoroethoxy)methylcyclopentane (21, 6% yield), and 16.5 mg of 1-(p-hydroxyphenyl)-1-(2,2,2-trifluoroethoxy)cyclohexane (22, 4% yield). Data for 21: 1 H NMR (CD3COCD3, from the mixture) δ 6.8-7.4 (AA′BB′, 4H), 4.1 (m, 1H), 3.7 (q, 2H, J ) 9 Hz), 2.2 (m, 1H), 1.1-1.8 (m, 8H); 13 C NMR (CD3COCD3) δ 156.7, 135.1, 135.0 (q, CF3, J ) 275 Hz), 127.3 (CH), 114.8 (CH), 87.4 (CH), 64.7 (q, CH2, J ) 35 Hz), 46.5 (CH), 35…”

“…In TFE. After 26 h of irradiation (80% conversion), purification (cyclohexane as the eluant) of the raw photolisate afforded 14 mg of 5 (11% yield) and a mixture containing 80 mg of 20 (29% yield) and 105 mg of p -methoxyphenylcyclohexane ( 23 , 45%). Data for 23 : 1 H NMR (CDCl 3 , from the mixture) δ 6.80−7.15 (AA‘BB‘, 4H), 3.77 (s, 3H), 3.15 (s, 3H), 2.10−2.20 (m, 2H), 1.20−1.80 (m, 8H); 13 C NMR (CDCl 3 ) δ 157.5, 140.3, 127.5 (CH), 113.6 (CH), 55.1 (CH 3 ), 48.3 (CH 3 ), 35.2 (CH 2 ), 29.0 (CH 2 ), 25.3 (CH 2 ), 25.0 (CH 2 ), 21.7 (CH 2 ); IR (neat, for the mixture) ν/cm -1 2928, 2855, 2363, 1610, 1512, 1247, 1178, 1037, 824; MS ( m / z ) 190 (M + , 60), 147 (100), 134 (30), 121 (56), 91 (45), 43 (45).…”

One-Pot Synthesis of Propargylamines Using Ag(I)-Exchanged K10 Montmorillonite Clay as Reusable Catalyst in Water

“…Montmorillonites clays are composed of negatively charged layers and an interlayer containing cationic species. The cationic species can be easily replaced by other metal polycations, and these ion-exchanged montmorillonites have great potential as solid acid catalysts. − Because of their tunable Bronsted and Lewis acidities, both natural and ion-exchanged clays function as efficient catalysts for various organic transformations . Hence, in the present work, we report an environmentally benign and highly efficient three-component A 3 coupling catalyzed by Ag I exchanged over K10 clay for the preparation of propargylamines via activation of alkyne in water.…”

Kumada Coupling of Aryl and Vinyl Tosylates under Mild Conditions.

“…1-Cyclohexyl-4-methoxy-benzene. 15 3.6 mg Pd(P(o-tol) 3 ) 2 (0.005 mmol), 2.7 mg 1 (0.005 mmol), 139 mg 4-MeOC 6 H 4 OTs (0.50 mmol) and 0.28 mL of a 2.0 M solution of cHexMgCl (0.550 mmol) in diethylether were used. The solution was stirred at room temperature for 16 hours.…”