The mechanism of the previously developed cross-coupling reaction of aryl Grignard reagents with aryl halides was explored in more detail. Single electron transfer from an aryl Grignard reagent to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle consists entirely of anion radical intermediates.

A new convenient, functional group-tolerant, transition metal-free route to aryl trifluoromethyl ketones under mild conditions is described. The reaction of not only aryl Grignard reagents carrying reducible electrophilic functional groups, such as ester and cyano groups, but also electron-deficient nitrogen-containing heteroaryl Grignard reagents with methyl trifluoroacetate gives the correspo...

[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nuc...

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups...

Selective functionalization reactions of aromatic and heteroaromatic halides with carbon, oxygen, and nitrogen nucleophiles have attracted much attention in the last decades. In addition to typical metal-catalyzed coupling reactions, direct functionalization of aryl halides through the formation of Grignard reagents offer new ways for the efficient construction of biologically interesting carbo...

The use of transition-metal catalysis to form new C C bonds is an important tool in organic synthesis. Palladiumand nickel-catalyzed C C bond-forming reactions have been extensively explored and are well understood. The use of iron as the catalyst has gained much less attention, despite the innovative work of Kochi et al. in the 1970s. Recently, several groups have turned their attention toward...

The synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic ring opening of the corresponding oxaphospholanes is described. Two representative substrates: the phosphonate 2-ethoxy-1,2-oxaphospholane 2-oxide and the phosphinate 2-phenyl-1,2-oxaphospholane 2-oxide were reacted with various Grignard reagents to produce a single alkyl/aryl product. These products ...

Catalytic cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing beta-hydrogens is achieved using Fe(III) amine-bis(phenolate) halide complexes.

The mechanism of the TEMPO mediated oxidative homo-coupling of aryl Grignard reagents is investigated in detail by experimental and computational studies. Experimental data reveal that the nitroxide-mediated homocoupling reaction of aryl Grignard reagents does not occur via free aryl radicals. Evidence for the presence of biaryl radical anions as intermediates in the coupling reaction is provid...

Homocoupling reactions of aryl, alkenyl, and alkynyl Grignard reagents are an easy and efficient access to symmetrical dior polyaromatic, olefinic, or acetylenic conjugated compounds. The potential applications of such compounds in optical materials, molecular devices, and organic conductors are well-recognized.1 Therefore, for large-scale applications, it is interesting to develop more conveni...