Reactions of the aryl complexes Rh(aryl){? 3 -P,O,P-[xant(P i Pr 2 ) ]} (1; = 3,5-Me C 6 H (a), 5 (b), 3,5-Cl (c), 3-FC 4 (d); xant(P 9,9-dimethyl-4,5-bis-(diisopropylphosphino)xanthene) with O , CO, and MeO CC?CCO Me have been performed. Under 1 atm pentane solutions afford dinuclear peroxide derivatives [Rh(aryl){? -P,P-xant(P }] (?-O (2a–2d) as yellow solids. In solution, these species are u...

Abstract An efficient stereocontrolled preparation of 2-substituted pyrrolidines and 5-substituted indolizidin-7-ones, by using chiral N-tert-butanesulfinyl imines derived from 4-halobutanal as starting materials, is detailed. Addition Grignard reagents a decarboxylative Mannich­ reaction with β-keto acids involving these proceeded high diastereoselectivity. The synthesis the pyrrolidinic alkal...

The reactions of the substituted 2,2':6,2''-terpyridine ligands, 4'-mesityl-2,2':6',2''-terpyridine (mesitylterpy) (1a), 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine (tri-(t)Buterpy) (1b) and 4'-phenyl-2,2':6',2''-terpyridine (phenylterpy) (1c) with Grignard reagents were investigated. When half an equivalent of mesitylterpy or tri-(t)Buterpy were treated with MeMgBr in diethyl ether, the on...

Racemic 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, the major and minor constituents, respectively, of the sex pheromone of Leucoptera coffeella, have been synthesized from citronellol in 56-58% overall yield through six steps. Ultrasound irradiation efficiently supported tosylation of alcohols (two steps) as well as the subsequent cross coupling reactions with the pertinent Grignard re...

An efficient user-friendly method of acylation of Grignard reagents to selectively synthesize ketones is presented, which is assisted by simple amides such as NMP, or DMF. The present chemoselective method tolerates a variety of functional groups such as ketone, ester, nitrile and other functional groups.

The new well-defined catalyst [Pd(μ-Cl)Cl(IPr*)]2 enables the efficient Grignard reagent cross-coupling for the synthesis of tetra-ortho-substituted biaryls. The high reactivity of the complex is associated with the important bulkiness of the IPr* ligand. The dimer represents the most efficient catalyst reported to date for this challenging transformation.

Magnesium-aryloxide and -amide compounds supported by amidinate ligands are accessible in two-steps from a suitable Grignard reagent. Both species are active for the dimerization of benzaldehyde. The slower initiation by the aryloxide was exploited in the isolation of a bis-mesitylaldehyde adduct.

Despite their enormous synthetic relevance, the use of polar organolithium and Grignard reagents is greatly limited by their requirements of low temperatures in order to control their reactivity as well as the need of dry organic solvents and inert atmosphere protocols to avoid their fast decomposition. Breaking new ground on the applications of these commodity organometallics in synthesis unde...