Synthesis of conjugated multi-ynamides by copper-catalyzed reactions

Abstract

International audienceThe synthesis of multi-ynamides according to the copper-catalyzed Evano’s and Hsung’s methods is described. In these new compounds, the ynamide functions are conjugated to each other with a phenyl, a biphenyl, a thienyl or a triphenylamine space

Reactivity of Functionalized Ynamides with Tetracyanoethylene: Scope, Limitations and Optoelectronic Properties of the Adducts

“…To evaluate the possibility to perform multiple TCNE additions on the same molecule, we treated conjugated bis-ynamides [22] with 2equivalents of TCNE under the same conditions as those previously described (Scheme 3). We startedw ith monophenylb is-ynamide 33,w hich was left to reacto vernight at room temperature with 2equivalents of TCNE.T he major product obtained was monoadduct 34 in 79 %y ield.…”

Quadruple Functionalization of a Tetraphenylethylene Aromatic Scaffold with Ynamides or Tetracyanobutadienes: Synthesis and Optical Properties

“…These two methods are nevertheless very complementary and allowed us to synthesize most of our targeted ynamides. [17][18][19][20][21][22]27] For Hsung conditions, the precursor is a brominated alkyne that is usually easily synthesized using a mixture of N-bromosuccinimide and silver nitrate in acetone at room temperature. The main limitation of Hsung's method is probably the possible poor stability of brominated alkynes when connected to an electrondonating group, as we observed in the past.…”

“…The main limitation of Hsung's method is probably the possible poor stability of brominated alkynes when connected to an electrondonating group, as we observed in the past. [22] This is the reason why we first considered the Evano's method, which starts with gem-dibromovinylic substrates, to tackle the synthesis of compound 1. Therefore, compound 5 was reacted with benzyltosylamide, copper iodide, cesium carbonate (Cs 2 CO 3 ) and dimethylethylenediamine (DMEDA) in dioxane at 60 °C for 17 hours.…”

“…[17,18] We are particularly interested in these TCBDs for their original optoelectronic properties, [19] and have thus been working on the conjugation of ynamides to π-systems, [20,21] which can pose a challenge when it comes to introducing two ynamide functions within the same molecule. [22] Even though the synthesis of ynamides is well documented, compounds bearing more than two ynamides (or ynamines) remain scarce. [23][24][25][26] We recently synthesized a tris-ynamide (1) conjugated to a triphenylamine and reacted it with TCNE to access compound 2 bearing three TCBD units (Figure 1a).…”

Recent Advances in the Synthesis of Ynamides

“…图式 30 铜盐和 1,10-菲罗啉体系下合成炔酰胺 Scheme 30 Synthesis of ynamides with the combination of Cu-salt and 1,10-phen 2015 年, Trolez 等 [44] 报道了多炔酰胺的合成. 借助 Hsung 和 Evano 合成炔酰胺的方法, 以炔溴为原料, 在 K 2 CO 3 、CuSO 4 和 1,10-菲罗啉的条件下, 与磺酰胺反应 生成双炔酰胺和三炔酰胺(Scheme 31).…”