A Novel Synthesis of α-Tellanyl α,β-Unsaturated Aldehydes Using α-Tellanyl β-Alkoxyalkenyl Lithiums

Abstract

β-Ethoxy-α-phenyltellanylvinyl lithiums were successfully generated in situ from phenyltellanylacetaldehyde diethyl acetal with lithium 2,2,6,6-tetrame-thylpiperidide (LTMP) and underwent methylation or nucleophilic addition with aldehydes and ketones. The successive dehydration of the allylic alcohols with trimethylsilyl trifluoromethanesulfonate (TMSOTf) gave α-phenyltellanyl α,β-unsaturated aldehydes, which transformed to some useful compounds.     

三氟甲基磺酸三甲基硅酯/四氯化钛复合体系引发 1, 3-戊二烯的阳离子聚合

研究了以三氟甲基磺酸三甲基硅酯[(CH~3)~3SiOSO~2CH~3,TMSOFf]为主引发剂,TiCl~4为共引发剂的复合引发体系对1,3-戊二烯(PD)的聚合行为。TMSOTf/TiCl~4复合体系引发PD不但比单独的TiCl~4引发具有更高的引发活性,而且提高了聚合物分子量,能把聚合反应速率提高8.8倍,把聚合物的收率从TiCl~4引发的62.5%提高到95%以上。对该复合体系聚合PD的动力学,反应机理所作的研究表明:TMSOTf和TMSOTf/TiCl~4都是通过它们与体系中残存水通过水解生成的质子酸引发进行的,聚合反应属一级反应。在该体系中加入酮类后,产率和分子量均降低,但均随着酮类的位阻的增加而增大。     

Lewis acid mediated reactions of cyclopropyl aryl ketones with arylaldehydes, facile preparation of 2-(2-hydroxyethyl)-1,3-diarylpropenones

In the presence of Lewis acid TMSOTf, ring-opening reaction of aryl cyclopropyl ketone with arylaldehyde took place under mild conditions to give 2-(2-hydroxyethyl)-1,3-diarylpropenone in good yield. By protection of hydroxy group with triethylsilyl group (TES), the corresponding ring-opened product 7 was obtained in high yield with good geometrical selectivity.     

Preparation of 3-arylmethylindoles as selective COX-2 inhibitors

The 3-arylmethylation of indoles using TMSOTf/Et₃SiH with a wide variety of substituted benzaldehydes has been accomplished. Under these mild Lewis acid mediated reductive conditions, it was demonstrated that indoles bearing both 6-MeSO₂ and 2-methyl substituents could be 3-arylmethylated in good to excellent yields to afford the corresponding 3-arylmethyl indoles, effective as selective COX-2 inhibitors. In addition, the viability of this method for the reductive alkylation of indoles by ketones was demonstrated and shown to be C-3 regioselective. For indoles bearing both a 6-MeSO₂ and 2-cyano substituent where this indole reductive alkylation methodology was unsuccessful, an unprecedented Pd(0) mediated arylorganozinc coupling with the requisite substituted 3-methylcarbonatomethylindole proved successful in affording the desired 2-cyano-6-MeSO₂-3-arylmethylindoles effective as selective COX-2 inhibitors.