Reactivity of β-Stannylketones. Elimination vs. Substitution 英文参考文献.docVIP

388 Molecules 2000, 5 Reactivity of β-Stannylketones. Elimination vs. Substitution Ana Paula Murray and Alicia B. Chopa* Instituto de Investigaciones en Química Orgánica, Universidad Nacional del Sur, Avda. Alem 1253 (8000) Bahía Blanca, Argentina Tel/Fax: 54 291 4595187, E-mail: achopa@criba.edu.ar *Author to whom correspondence should be addressed. Abstract: In the present work we report the results obtained in the reaction of β- stannylketones (I) with t-BuONa in dimethylsulfoxide (DMSO) and acetonitrile (ACN) as solvents. The reaction mechanisms probably involved are proposed. Introduction In the reaction of β-functionalized organotin compounds (I) with t-BuONa in t-BuOH there is a competition between an elimination reaction [(E1cB)R], leading to olefins with high diastereoselectiv- ity, and a nucleofilic substitution reaction yielding the reduction product (II) [1]. Now we report on the reactions of β-stannylketones (I) with t-BuONa in DMSO and ACN in order to compare the reactivity in these solvents. R1 Ph H R1 Z tBuONa Z R3-nXnSn + Ph Z DMSO R1 II Ph I or ACN Z / E Z = COPh, CN ; R1 = Me, Ph ; R = Me, Ph ; X = Cl, Br ; n = 1, 3 Experimental Anhydrous solvents and sublimated t-BuONa were used. The β-stannylketones were synthesized in our laboratory [2-3]. The reaction mixtures were analysed by CGL. The reaction conditions are de- tailed in the Table.  389 Molecules 2000, 5 Results and Discussion The results summarised in the Table show that these reactions lead to higher yields in shorter reac- tion times, depending on the substrates. Thus, while β-stannylketones carrying electron-withdrawing groups attached to tin lead to the elimination product in high yield, β-trialkylstannylketones give mainly the reduction product. Table. Reactions of R3-nXnSn-CH(Ph)-CH(R1)-COPh with tBuONaa. R1 N° R3-nXnSn DMSO ACN % Elim (Z/E) % Elim (Z/E) 1 2 3 4 5 6 7 8 9 Me Me Me Me Me Me Ph Ph3Sn Ph3