Grignard cross-coupling

Carbon-Chiral Allylsilanes by Asymmetric Grignard Cross-Coupling... 

Geranyltrimethylsilane, 142 Grignard cross-coupling, asymmetric, 31 Grignard reaction, 39,63 Grignard reagent, 45,58,120,121... 

Yamano T, Taya N, Kawada M, Huang T, Imamoto T (1999) Tetrahedron Lett 40 2577 Brunner H, Nishiyama H, Itoh K (1993) Asymmetric hydrosilylation. In Ojima I (ed) Catalytic asymmetric synthesis. Wiley-VCH, New York, chap 6 Sawamura M, Kuwano R, Ito Y (1994) Angew Chem, Int Ed Engl 33 111 Kuwano R, Uemura T, Saitoh M, Ito Y (1999) Tetrahedron Lett 40 1327 Hayashi T (1993) Asymmetric allylic substitution and grignard cross-coupling. In Ojima I (ed) Catalytic asymmetric synthesis. WUey-VCH, New York, chap 7-1 Trost BM, Vranken DLV (1996) Chem Rev 96 395 Consiglio G,Waymouth RM (1989) Chem Rev 89 257... 

Figure 3.49. Chiral ligands that exhibit high enantioselectivity in the nickel-catalyzed Grignard cross-coupling reaction of vinyl bromide (or chloride) with 1-phenylethylmagne-sium chloride.

Asymmetric Grignard Cross-Coupling Catalyzed by Chiral... 

More recent review Hayashi, T. Asymmetric Grignard Cross-Coupling Catalyzed by Chiral Phosphine-Nickel and Phosphine-Palladium Complexes, in Asymmetric Reactions and Processes in Chemistry (Eliel, E. L., Otsuka, S. ed.), American Chemical Soc. Symp. Series Vol. 185, p. 177 (1982)... 

The ionic liquid butylmethylimidazolium tetrachloroferrate (bmim-FeCU) has been found to be a very effective and completely air-stable catalyst for the biphasic Grignard cross-coupling with primary and secondary alkyl halides bearing /3-hydrogens.93 The ionic liquid catalyst has been successfully recycled four times. 

Aryl O-Carbamate and S-Thiocarbamate-Grignard Cross-Coupling Reactions... 

Scheme 32. Indole 5-O-carbamate-Grignard cross-coupling annelation via indole 4,5-quinodimethide.

In addition to iron, recent uses of manganese, chromium, and cobalt catalysts for Grignard cross-coupling are described in the Shinokubo-Oshima review. ... 

Since Stille reported Pd-catalyzed coupling reactions between unsaturated halides and sulfonates with organostannanes (Scheme 1-16) [134], there have been many mechanistic studies on these and related reactions [135 —137], A commonly accepted mechanistic pathway resembles that of Grignard cross-coupling, which requires an... 

A further advantage is the possible in situ generation of catalysts from simple metal salts or complexes (e. g., Ni(OR)2, PdCU) and azolium salts. The nickel-catalyzed Grignard cross-coupling of aryl chlorides at room temperature [123] and the activation of aryl fluorides [136] are convincing examples. 

Banno, T., Hayakawa, Y., Umeno, M. Some applications of the Grignard cross-coupling reaction in the industrial field. J. Organomet. Chem. 2002, 653, 288-291. 

Ditertiary phosphines such as (86), (92), and (98) (100) (Scheme 6) have found important uses as ligands for metal-catalyzed transformations, including e.g., palladium-catalyzed Grignard cross couplings,194,205 rhodium-catalyzed Michael additions,2 hydrocyanations,206 copolymerizations,20 and palladium-catalyzed animations.208 Rhodium complexes of (86) are catalysts for the carbonylation of methanol.188 More recently the ligand bite angle of ditertiary phosphines such as (100) has been shown to influence catalytic activity/selectivity in several important catalytic processes.209-213... 

---