邻羟基苯丙酮衍生的烯醇钛试剂非对映选择性反应及O磺酰基肟的合成-有机化学专业论文.docx

甲苯磺酰基肟的有效方法，产率达到、反应条件温和、产率较高、后处理 甲苯磺酰基肟的有效方法，产率达到 、反应条件温和、产率较高、后处理 ，非对映立体选择性，N．对甲苯磺酰 Il ABSTRACTThe ABSTRACT The diastereoselective reactions of chlorotitanium enolate derived from 2-hydroxypropiophenone and synthesis of O—sulfonyl oximes have been exploited in this dissertation，which is divided four parts．The main results are summarized as below． 1．Diastereoselective aldol reactions of chlorotitanium enolate derived from 2-hydroxypropiophenone are exploited．The corresponding titanium enolates were generated directly by treating 2-hydroxypropio- phenone with in turn TICl4 and i-Pr2NEt in methylene chloride at一20 oC under N2，followed by the reaction of the chlorotitanium enolate with aldehydes to yield 13-hydroxy ketones in 53-93％yields with good to excellent syn selectivity．The corresponding aldol products were prepared in lower velocity with better diasteroselectivity when using another equivalent of Lewis acid such as AICl3．Surprisingly,Utilization of trans- cinnamaldehyde，4-methoxybenzaldehyde and 4-butoxybenzaldehyde in the aldol reaction afforded mainly unexpected anti aldol adducts．Three reasonable transition states for the reactions have been assigned to explain the diastereochemical outcome of the process depending on substitution pattern on aldehydes． 2．Mannich-type reaction of the titanium enolate derived from 2-hydroxypropiophenone with N-tosylimines has been studied．The III corresponding corresponding titanium enolates were generated directly by treating 2-hydroxy or alkyloxy propiophenone with in turn TICl4(1 equiv)and i-Pr2NEt(2．0 equiv)in methylene chloride at-20 oC．The reaction of the enolate titanium with N-tosylimines provided the corresponding 13-amino ketones in good to excellent yields(60-90％)and with99：1 anti diastereoselectivity．High anti selectivity is not independent of the electron-·donating and electron·-withdrawing groups on the phenyl ring of the N-tosylimines．Noteworthy is the observation that the influence of a second Lewis