Gas-phase carbanion rearrangements. Does the Wittig rearrangement occur for deprotonated vinyl ethers?
作者:Peter C. H. Eichinger、John H. Bowie
DOI:10.1039/p29900001763
日期:——
Deprotonation of alkyl vinyl ethers (CH2CHOR) with NH2– in the gas phase yields the two carbanions CH2OR and –CHCHOR. The former ion can be synthesized specifically using the SN2(Si) reaction CH2C(SiMe3)OR + NH2–→CH2OR + Me3SiNH2: the ion undergoes several competitive and characteristic collision-induced reactions. For example, (i) when R Et, elimination of an alkene, i.e. CH2OR→(CH2CHO)–+(R–H), and
烷基乙烯基醚(CH去质子化2 CHOR)与NH 2 -在气相产率两个碳负离子CH 2 OR和- CH CHOR。前者离子可以特异性使用S来合成Ñ 2(Si)的反应CH 2 C(森达3)OR + NH 2 - →CH 2 OR +我3的sinh 2的离子经历几个竞争性和特性碰撞诱导反应:。例如,(i)当R Et时,消除烯烃,即。CH 2 OR→(CH 2 CHO)–+(R–H),和(ii)Wittig重排CH 2或[未显示图形] CH 2 C(R)O –。