The acid-base adducts ( and ) as the ionic salts in the format of [2H][OTf], derived from the neutralization of -butyl-substituted diphosphines [: 1,2-bis[(di--butylphosphanyl)methyl]benzene; : 4,5-bis(di--butylphosphino)-9,9-dimethylxanthene] with triflic acid (HOTf, CFSOH), were synthesized, characterized, and then applied in Pd-catalyzed methoxycarbonylation-aminolysis tandem reaction for the synthesis of linear primary amides. For the first time, the structural configurations of such adducts were deconvoluted by the single crystal X-ray diffraction analysis. In , the two P-H bonds were distinct, and one of the P-H bond was hydrogen-bonded with CFSO-anion whereas the two P-H bonds in were equivalent without hydrogen-bond effect. became more robust against moisture and oxygen than its counterpart of due to the available hydrogen-bond interaction whereas became more labile in comparison to . When was applied in Pd-catalyzed methoxycarbonylation-aminolysis tandem reaction, the linear primary amides were obtained in the yields of 69–84% whereas led to the poor result. It was found that Pd(OAc) system not only successfully catalyzed the first-step methoxycarbonylation of alkenes to generate the carboxylic esters with L/B > 90/10 by predominantly following -Markovnikov’s rule, but also accelerated the second-step aminolysis.

中文翻译：

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叔丁基取代二膦与三氟甲磺酸加合物：合成、表征及其在 Pd 催化甲氧基羰基化-氨解串联反应中的应用

酸碱加合物 ( 和 ) 为离子盐，形式为 [2H][OTf]，由正丁基取代的二膦 [: 1,2-双[(二-丁基膦酰基)甲基]苯中和而得; : 4,5-双(二丁基膦)-9,9-二甲基呫吨]与三氟甲磺酸(HOTf, CFSOH)的合成、表征，然后应用于Pd催化的甲氧基羰基化-氨解串联反应中合成线性伯酰胺。首次通过单晶 X 射线衍射分析对此类加合物的结构构型进行解卷积。在 中，两个 PH 键是不同的，其中一个 PH 键与 CFSO-阴离子形成氢键，而 中的两个 PH 键是等价的，没有氢键作用。由于可用的氢键相互作用，变得比其对应物对湿气和氧气更强大，而与 相比变得更不稳定。当应用于Pd催化的甲氧基羰基化-氨解串联反应时，线性伯酰胺的收率在69%~84%之间，但结果较差。结果发现，Pd(OAc)体系不仅主要遵循马尔可夫尼科夫规则成功催化了烯烃的第一步甲氧基羰基化反应生成L/B > 90/10的羧酸酯，而且加速了第二步氨解反应。