Thomas C. Flood

Trimethylsilyl-substituted diazoalkanes : I. Trimethylsilyldiazomethane

Abstract Trimethylsilyldiazomethane was prepared by the action of aqueous KOH on nitroso-N-(trimethylsilylmethyl)urea. The spectroscopic properties of this stable, greenish-yellow liquid which can be isolated by gas chromatography are discussed. Its reaction with acetic acid gives the expected CH3CO2CH2SiMe3 in addition to SiC cleavage products, CH3CO2CH3 and CH3CO2SiMe3. Products of the 1,3-dipolar addition of Me3SiCHN2 to activated olefins were not very stable, and only the adduct with acrylonitrile was isolated as a pure material Trimethylsilyldiazomethane undergoes Me3SiCH transfer to olefins, giving trimethylsilyl-substituted cyclopropanes, in the presence of CuCI in benzene, but other products are formed as well. Thus such a reaction with cyciohexenegave anti-7-trimethylsilylnorcarane (65%), syn-7-trimethylsilylnorcarane (7%), cis- and trans-l,2-bis(trimethylsilyl)ethylene (9% and 13%, respectively), and an unidentified Me3SiCH trimer (2.3%).

Intra- and intermolecular activation of carbon-hydrogen bonds in a tetrakis(trimethylphosphine)osmium(II) system

Activation des liaisons C-H, de facon intramoleculaire ou intermoleculaire par un intermediaire genere par thermolyse du cis-L 4 Os(H)R avec L=(CH 3 ) 3 P et R=CH 3 , CH 2 C(CH 3 ) 3 et CH 2 Si(CH 3 ) 3

A novel route to δ,ε-unsaturated-α-ketocarboxylic acid esters via ring opening of 6-trimethylsilylmethyl-5,6-dihydro-4H-1,2-oxazines

6-Trimethylsilylmethyl-5,6-dihydro-4H-1,2-oxazines, which are prepared by the reaction of α-halogeno-oximes with allylsilanes in the presence of anhydrous sodium carbonate, are converted into δ,Iµ-unsaturated-α-ketocarboxylic acid esters by the action of mineral acids.

General synthesis of optically pure chiral iron primary alkyls via a metal-activated alkylation reagent

Preparation of the optically pure alkylation reagent (3) and its reaction with Grignard and alkyl-lithium reagents provides a general route to iron alkyls whose enantiomeric purity may be shown by the n.m.r. spectra of their SO2 insertion products.