Nickel-catalyzed alkenyl aryl coupling

Phenylurefbanes, 58, 10 Phosgene, 57, 46 Phosphine, diphenyl-, 56,45 Phosphine-mckcl catalyst, 58, 129 PHOSPHINE-NICKEL CATALYZED COMPLEX CROSS-COUPLING OF GRIG-NARD REAGENTS WITH ARYL AND ALKENYL HALIDES, 58, 127 Phosphine, phenyl-, bis(3-dimethylamino-piopyl)-, 55, 128 Phosphine, triphenyl-, 56, 81 Phosphomum, [ 4-(4-rne thoxy phenyl)-2-butenyl) triphenyl, iodide, 56, 81 Phosphomum, 2-octadecenyltnphenyl-, iodide, 56, 81... 

Negishi, E., Baba, S. Novel stereoselective alkenyl-aryl coupling via nickel-catalyzed reaction of alkenylalanes with aryl halides. J. Chem. Soc., Chem, Commun, 1976, 596-597. 

R = alkenyl, aryl, allyl, benzyl, propargyl R = alkenyl, aryl, alkynyl, alkyl, benzyl, allyl The Negishi Coupling was the first reaction that allowed the preparation of unsymmetrical biaryls in good yields. The versatile nickel- or palladium-catalyzed coupling of organozinc compounds... 

Other coupling partners to organozinc reagents include heterocyles such as 2-methylthiobenzothiazole, alkenyl aryl iodonium triflates (alkenyl group transfer for synthesis of trisubstituted alkenes), and aryl heteroaryl ethers. " Improved nickel-catalyzed cross-coupling conditions between oz-rto-substituted aryl iodides-nonaflates and alkyl-zinc iodides in. solution and in the solid phase have been defined. ... 

Ni-Catalyzed Reactions The nickel-catalyzed cross-coupling of alkenyl Grignard reagents with aryl nitrile derivatives has been exploited by Miller and coworkers [4]. The conditions are similar to those described in Scheme 22.2. In general, alkenyl Grignards were /Zmixtures and therefore provided styrene derivatives as a mixture of E and Z isomers in modest to good yields (43-80%). Milder conditions were later developed in the Ni-catalyzed arylcyanation of alkynes, in which the insertion of alkynes into an aromatic C-CN bond took place (Scheme 22.12a) [5, 21a, b]. The intramolecular version of the reaction was likewise reported, and cyclization in a 5-exo-dig fashion occurred (Scheme 22.12b) [21c]. The addition of Lewis acids, such as AlMe Cl, AlMe, and... 

Miller, J. A., Dankwardt, J. W. (2003). Nickel catalyzed cross-coupling of modified alkyl and alkenyl Grignard reagents with aryl- and heteroaryl nitriles activation of the C—CN bond. Tetrahedron Letters, 44, 1907-1910. 

Scheme 1.55 Nickel-catalyzed Negishi-Baba cross-coupling arylation of aryl/alkenyl pivalates [177].

The nickel-catalyzed Suzuki-Miyaura-type C-O bond arylation has been successfully applied to steroidal architecture (Scheme 4). A hydroxyl moiety in estrone can readily be substituted by an array of aryl groups under nickel catalysis via conversion into pivalate instead of the typically used triflate [38]. The carbonyl moiety in estrone also serves as a suitable precursor for an alkenyl C-O electrophile. Treatment of estrone with 2-propenyl acetate affords the compounds bearing two acetate groups, both of which are potentially reactive toward nickel-catalyzed cross-coupling. However, selective arylation took place at the alkenyl position, and... 

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