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Impact of Precatalyst Activation on Suzuki-Miyaura Catalyst-Transfer Polymerizations: New Mechanistic Scenarios for Pre-transmetalation Events
ACS Macro Letters ( IF 5.1 ) Pub Date : 2017-10-25 00:00:00 , DOI: 10.1021/acsmacrolett.7b00696
Roberto Grisorio 1, 2 , Gian Paolo Suranna 1, 2
Affiliation  

The relevance of LnPdX2 precatalyst activation on the Suzuki-Miyaura reaction course was investigated in the case of catalyst-transfer polymerizations. A catalytic study, backed up by theoretical calculations, allowed to ascertain the coexistence of a neutral and an anionic mechanistic pathways in the precatalyst activation, in which the bulky tBu3P external ligand plays a crucial role. The fine-tuning of the catalytic conditions can steer the activation step toward the anionic pathway, leading to the full control over the polymerization course. While providing insights and perspectives into the catalyst-transfer polymerizations, these results uncover unexplored scenarios for the pre-transmetalation events of Suzuki-Miyaura reactions contributing to its full understanding.

中文翻译:

预催化剂活化对 Suzuki-Miyaura 催化剂转移聚合的影响:预转移事件的新机制情景

在催化剂转移聚合的情况下,研究了 L n PdX 2预催化剂活化对 Suzuki-Miyaura 反应过程的相关性。一项由理论计算支持的催化研究可以确定在催化剂前活化过程中中性和阴离子机制途径的共存,其中庞大的t Bu 3P外部配体起着至关重要的作用。催化条件的微调可以将活化步骤转向阴离子途径,从而完全控制聚合过程。在提供对催化剂转移聚合的见解和观点的同时,这些结果揭示了 Suzuki-Miyaura 反应的前金属化事件未探索的场景,有助于对其进行全面理解。
更新日期:2017-10-25
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