Leaving group weak bases

The rates of both Sn2 and SnI reactions are influenced by the nature of the leaving group. Weak bases are the best leaving groups because weak bases are best able to accom-... 

R can be a variety of stmctures. Z is a leaving group and typically the conjugate base of a weak acid whose piC can range from 5 to 20 (86). The hydrogen peroxide is typically incorporated into the bath by a dding a soHd source of peroxide such as sodium percarbonate or the mono- or tetrahydrate of sodium perborate (86). 

In the El mechanism, the leaving group has completely ionized before C—H bond breaking occurs. The direction of the elimination therefore depends on the structure of the carbocation and the identity of the base involved in the proton transfer that follows C—X heterolysis. Because of the relatively high energy of the carbocation intermediate, quite weak bases can effect proton removal. The solvent m often serve this function. The counterion formed in the ionization step may also act as the proton acceptor ... 

Secondary alkyl halides Sjvj2 substitution occurs if a weakly basic nucleophile is used in a polar aprotic solvent, E2 elimination predominates if a strong base is used, and ElcB elimination takes place if the leaving group is two carbons away from a carbonyl group. Secondary allylic and benzyiic alkyl halides can also undergo S l and El reactions if a weakly basic nucleophile is used in a pro tic solvent. 

In order to explain the selective cleavage of the C O bond, one has to take into account two factors (i) the oxonium is a better leaving group than the sulfonium (ii) for a nucleophilic substitution, weak bases are better leaving groups. The proposed mechanism follows Scheme XXI [99, 104] ... 

However, the E2C mechanism has been criticized, and it has been contended that all the experimental results can be explained by the normal E2 mechanism. McLennan suggested that the transition state is that shown as 18. An ion-pair mechanism has also been proposed. Although the actual mechanisms involved may be a matter of controversy, there is no doubt that a class of elimination reactions exists that is characterized by second-order attack by weak bases. " These reactions also have the following general characteristics (1) they are favored by good leaving groups (2) they are favored by polar aprotic solvents (3) the reactivity order is tertiary > secondary > primary, the opposite of the normal E2 order (p. 1319) (4) the elimination is always anti (syn elimination is not found), but in cyclohexyl systems, a diequatorial anti elimination is about as favorable as a diaxial anti elimination (unlike the normal E2 reaction, p. 1302) (5) they follow Zaitsev s rule (see below), where this does not conflict with the requirement for anti elimination. 

Protonation, if forced upon pyrrole, is found to take place not on nitrogen but on the a-carbon atom (19). This occurs because incorporation of the nitrogen atom s lone pair of electrons into the aromatic 6jre system leaves the N atom positively polarised protons tend to be repelled by it, and are thus taken up by the adjacent a-carbon atom. The basicity situation rather resembles that already encountered with aniline (p. 70) in that the cation (19) is destabilised with respect to the neutral molecule (18a). The effect is much more pronounced with pyrrole, however, for to function as a base it has to lose all aromatic character, and consequent stabilisation this is reflected in its related pKa (-0-27) compared with aniline s of 4-62, i.e. pyrrole is a very weak base indeed. It can in fact function as an acid, albeit a very weak one, in that the H atom of the NH group may be removed by strong bases, e.g. eNH2 the resultant anion (20) then retains the aromatic character of pyrrole, unlike the cation (19) ... 

Silicon and phosphorus generally form rather weak bonds, consequently in phosphorus chemistry, silyl substituents are mainly used as a leaving group. In silicon chemistry, phosphorus-based substituents are less common, though this has changed in the last two decades due to novel concepts in molecular chemistry (prominent examples are [/BuSi-P]4 [1] and R2Si=PR [2]) and in materials sciences. 

This reaction take place cause the leaving group is a weak base. 

SN1 Very strong effect reaction favored by polar solvents Weak effect reaction favored by good nucleophile/weak base Strong effect reaction favored by good leaving group Strong effect reaction favored by 3°, allylic, and benzylic substrates... 

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