Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes
Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes
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DOI：
10.1515/pac-2019-0214
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发表时间：
2019-12
影响因子：
1.8
通讯作者：
M. Quirós;E. Gómez-Bengoa;M. Muñoz
中科院分区：
文献类型：
--
作者：
M. Quirós;E. Gómez-Bengoa;M. Muñoz
摘要本文通过实验和计算方法研究了铂催化烯丙二氢烷氧基化生成缩醛的机理。我们的研究结果进一步解释了铂和金-乙烯基中间体在第一次亲核攻击后对配位烯的反应性差异，并提供了与铂的催化循环的新细节，揭示了烯醇醚作为催化循环的静息状态，当使用中性铂配合物时，在第二次亲核攻击后，通过Pt(IV) - h的SEOx过程作为最后的原金属分解步骤。当使用阳离子铂配合物时，快酸促进甲醇向烯醚的加成。
Abstract The mechanism of the platinum-catalysed dihydroalkoxylation of allenes to give acetals has been studied experimentally and by computational methods. Our findings further explain divergent reactivity encountered for platinum- and gold-vinyl intermediates after the first nucleophilic attack onto the coordinated allene, as well as provide new details on the catalytic cycle with platinum, uncovering enol ethers as resting states of the catalytic cycle, a SEOx process via Pt(IV)–H as the final protodemetallation step after the second nucleophilic attack when neutral platinum complexes are used, and a fast acid promoted addition of methanol to enol ethers when cationic platinum complexes are employed.