Reactivity of mixed organozinc and mixed organocopper reagents. Part 4: a kinetic study of group transfer selectivity in C?C coupling of mixed diorganocuprates

The competitive rate data and Taft relationships for the coupling of bromomagnesium n‐butyl (substituted phenyl) cuprates with alkyl bromides show that selective n‐butyl transfer can be explained by an oxidative addition mechanism. Taft reaction constants also show that the residual group FG‐C₆H₄ in the mixed cuprate n‐Bu(FG‐C₆H₄)CuMgBr changes the ability of the copper nucleophile to react with the electrophile RBr. These results provide support for the commonly accepted hypothesis regarding the dependence of the R¹ group transfer ability on the strength of R²? Cu bond in reactions of R¹R²CuMgBr reagents. Copyright © 2009 John Wiley & Sons, Ltd.     

On the mechanism of the N,N‐dimethyl amination of Grignard reagents: a kinetic study

A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N‐dimethyl O‐(mesitylenesulfonyl)hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a S_N2 displacement involving the attack of carbanions to sp³N in the amination reagent (AR). Copyright © 2007 John Wiley & Sons, Ltd.     

Reactivities of mixed organozinc and mixed organocopper reagents. Part 7. Comparison of the transfer rate of the same group in allylation of mixed and homo diorganozinc reagents

A detailed direct kinetic study has been carried out to compare the reaction rate of transferable group, Ph in mixed phenylzinc reagents, RPhZn (R = n‐alkyl) and in homo diphenylzinc reagent, Ph₂Zn in their reactions with allyl bromide in THF at 25–(?15) °C. Empirical rata law and activation parameters are consistent with a second‐order substitution reaction. The allylation rate of transferable group Ph in RPhZn (R = n‐alkyl) has been found higher than the rate of Ph group in Ph₂Zn. A mechanism which accommodates the kinetic data and higher allylation rate of transferable group Ph in RPhZn than that in Ph₂Zn is given. Copyright © 2013 John Wiley & Sons, Ltd.     

Kinetic role of t-amines in the ligand inhibited osmium tetraoxide catalyzed trimethylamine-N-oxide dihydroxylation of alkenes

Kinetic studies on the t-amine inhibited catalytic OsO₄ dihydroxylation of cyclooctene, octene, styrene and 4-methyl-, 4-methoxy-, 4-chloro-, 4-(chloromethyl), 4-(trifluoromethyl) and 3-chloro-derivatives of styrene with Me₃NO in t-BuOH have been carried out at 50 °C. The reactions follow identical kinetics: first order in total osmium species, first order in Me₃NO and zero order in alkene. All t-amines have been found to retard the catalysis and the reaction order in t-amine changes from inverse first order to zero. The involvement of dioxomonoglycolataosmium(VI) esters and their monoamine adducts in the rate-determining oxidation step was established by the linear plots of 1/k ₂ versus. 1/[L] where k ₂ is the decrease in second order rate constant in the presence of [L] concentration of t-amine ligand. Beyond a definite concentration of t-amine, the rate reaches a minimum and remains constant. Activation parameters were evaluated for catalytic OsO₄ dihydroxylation of 4-(chloromethyl)styrene at different t-amine concentrations. The values of H and S are consistent with the proposed mechanism.     

Leaving group effect in the sulfonyl transfer reactions of aryl benzenesulfonates with Grignard reagents

The C–S coupling reactions of aryl benzenesulfonates with phenylmagnesium bromide in THF:toluene (7:10) at 90 °C have been studied. A Hammett-type kinetic study of the leaving group effect of aryloxy groups provides a conclusive support for a two step addition-elimination mechanism in which C–S bond formation is rate determining step.     

Reactivity of mixed organozinc and organocopper reagents. 3. Atom economic electrophilic amination of methyl arylzinc reagents

Reaction of methyl arylzincs with acetone O‐(mesitylenesulfonyl)oxime in THF in the presence of CuCN at room temperature is efficient in selective electrophilic amination of aryl carbanions. This procedure allows for the preparation of arylamines in moderate to good yields and provides an efficient and atom economic alternative to existing amination methods for diarylzincs. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics and mechanism of the C-S coupling reactions of aryl Grignard reagents with aryl arenesulfonates

The kinetics of the C-S coupling of arylmagnesium bromides with phenyl tosylate has been studied in THF: toluene at 90°C. The reaction is first order in Grignard reagent and first order in phenyl tosylate. Kinetic data, Hammett relationship and activation parameters are consistent with a nucleophilic addition mechanism involving rate determining attack of carbanion to sulfonyl group followed by a fast phenoxide group leaving.      

Kinetic role of tert-amines in the osmium tetroxide catalyzed trimethylamine N-oxide dihydroxylation of cyclohexene

Effect of some tert-amines on the catalytic osmium tetroxide dihydroxylation of cyclohexene in aqueous tert-butyl alcohol has been investigated All amines have been found to retard the catalysis greatly and beyond a definite concentration of amine, the rate reaches a minimal and remains constant. The oxidation of cyclohexene is inhibited by pyridine, 2.2′-bipyridyl and DABCO with an inverse first-order dependence whereas inhibition by triphenylamine NN-diethylaniline, picoline pyrazine hexamethylenetetraamine and TMEDA shows an inverse partial order dependence. The inolvement of dioxomonoglycolatoosmium(VI) esters and their monoamine adducts in the rate determining oxidation step was established by the linear plots of 1/Δk₂ vs. 1/[L] where Δk₂ is the decrease in the second-order rate constant in the presence of [L] concentration of tert-amine. The ligand-accelerated or ligand-decelerated catalysis of tert-amines in the catalytic osmium tetraoxide dihydroxylation of alkenes may vary depending on the secondary oxidant on the alkene and on the structure and concentration of the tert-amine. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 359–366, 1997     

Competitive kinetic study of the amination of organomagnesium and ‐zinc reagents with acetone O‐sulfonyloxime

Kinetic studies are reported for the electrophilic amination of substituted phenylmagnesium bromides and CuCN‐catalyzed phenylzinc chlorides with acetone O‐(2,4,6‐trimethylphenylsulfonyl)oxime in tetrahydrofuran at reflux temperature and at room temperature respectively. Substituent effects were determined by competition experiments. Rate data are analyzed via Hammett relationships to support the proposed mechanisms for the substitution of these organometallics with an electrophilic amino transfer reagent. Copyright © 2005 John Wiley & Sons, Ltd.