Tremorine and precursors of gemini surfactants were synthesised in a one‐pot, three‐step, double‐catalytic A³ coupling reaction and characterised by structural and spectroscopic methods. The cationic [Au^I(L1)]SbF₆ complex is a more active catalyst compared to neutral L2– and L3–Au^I bis(trifluoromethanesulfonyl)imidate complexes (L1, L2=Buchwald‐type biaryl phosphane; L3=triphenylphosphine) in promoting the double A³ coupling of ethynyltrimethylsilane, secondary amines (cyclic, aliphatic, or aromatic) and formaldehyde. The solvent influences the catalytic performance by desilylation of silyl acetylene or deactivation of the catalyst by a halide anion. Acetylide‐bridged cationic digold(I) L1 and L2 complexes were isolated and characterised by means of single‐crystal X‐ray structure analysis and their spectroscopic properties. Iodine in the acetylene reagent deactivates the Au^I catalyst by formation of the less active iodido‐bridged cationic digold(I) L1 complex, which was fully characterised by single‐crystal X‐ray crystal structure analysis and spectroscopy. The nature of the phosphine ligand of the gold complexes used as catalyst affects the stability and activity of the formed cationic ethynyl‐bridged Au^I₂–L intermediates, isolation of which lends support to the proposed double A³ coupling mechanism.

中文翻译：

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阳离子乙炔基桥联二甲双胍催化剂制备Tremorine和Gemini表面活性剂前体

在一个单锅，三步，双催化A ³偶联反应中合成了Tremorine和Gemini表面活性剂的前体，并通过结构和光谱方法对其进行了表征。阳离子[Au ^I（L1）] SbF ₆络合物与中性L2–和L3–Au ^I双（三氟甲磺酰基）亚氨酸酯络合物（L1，L2 =布赫瓦尔德型联芳基膦； L3 =三苯膦）相比，具有更高的活性。双A ³乙炔基三甲基硅烷，仲胺（环状，脂肪族或芳香族）与甲醛的偶联。溶剂通过甲硅烷基乙炔的甲硅烷基化或通过卤化物阴离子使催化剂失活而影响催化性能。分离并通过单晶X射线结构分析及其光谱性质对乙炔桥联的阳离子digold（I）L1和L2络合物进行了表征。乙炔试剂中的碘通过形成活性较低的碘代桥联阳离子digdig（I）L1络合物而使Au ^I催化剂失活，该络合物通过单晶X射线晶体结构分析和光谱学得到充分表征。用作催化剂的金配合物的膦配体的性质会影响所形成的阳离子乙炔基桥联的Au ^I的稳定性和活性_{2 –} L中间体，通过隔离可以为拟议中的双A ³偶联机理提供支持。