Geminal dimetallic compounds

Relative Population of S-Form and F-Form Conformers of Bryonolic Acid and Its Derivatives in Equilibrium in CDCl3 Solutions.

“…The reaction mixture was treated as described above to give pure 7. Compound 8 According to the Cainelli procedure 19) based on the Wittig reaction, under an argon atmosphere, methylene iodide (66 mg, 0.24 mmol) in Et 2 O was added to a solution of 2 (100 mg, 0.22 mmol) and magnesium amalgam (8 g) in Et 2 O, and the entire mixture was stirred under reflux for 3 h. The reaction mixture was poured into 5% HCl and shaken with benzene. The combined organic layer was washed with H 2 O and evaporated to obtain the residue.…”

Structure and reactivity of bis(iodozincio)methane solution

“…These points can be overcome by use of a gem-dimetal compound or a metal carbene complex [3,4]. Cainelli and co-workers [5] had reported methylenation of ketones and aldehydes with gem-dimagnesium reagent which was prepared from diiodomethane and Mg/Hg in ether. More conveniently, Fried and co-workers [6] and Miyano and co-workers [7] demonstrated that treatment of diiodomethane with excess zinc gives gem-dizinc species in their Wittig-type methylenation reaction.…”

Nuclear magnetic resonance investigation of the conformational dynamic properties of benzocycloheptenones and related compounds

“…Compound 6-dG was prepared from the above sample of 5-d, by the reaction of methylene iodide and magnesium amalgam as previously described by Bertini et al (28). An ether solution (20 ml) of 0.50 g (3.0 mmol) of ketone 5-d, and 0.88 g (3.3 mmol) of methylene iodide was added with stirring, at room temperature under a nitrogen atmosphere, to previously prepared magnesium amalgam (0.160 g of Mg and 5 ml of Hg).…”

“…An ether solution (20 ml) of 0.50 g (3.0 mmol) of ketone 5-d, and 0.88 g (3.3 mmol) of methylene iodide was added with stirring, at room temperature under a nitrogen atmosphere, to previously prepared magnesium amalgam (0.160 g of Mg and 5 ml of Hg). After reaction work-up (28) and evaporation of the ether solvent, a vpc analysis of the crude product revealed a mixture of 6-dG (70%) and the starting ketone (30%). Cheinically pure 6 -4 was obtained by preparative vpc and its deuterium decoupled 'Hmr spectrum (10% in CHF,CI) showed a characteristic singlet at S 4.7 (C=CH2) aild another signal a t 6 2.8 (benzylic CH2CD, and CHDCD2) in the ratio 2:2.2.…”