Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions.
Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions.
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DOI：
10.1021/jacs.7b02232
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发表时间：
2017-06-14
影响因子：
15
通讯作者：
Smith MR 3rd
中科院分区：
文献类型：
--
作者：
Chattopadhyay B;Dannatt JE;Andujar-De Sanctis IL;Gore KA;Maleczka RE Jr;Singleton DA;Smith MR 3rd
本文介绍了一种在Ir催化的酚类C-H硼化反应中影响邻位和Meta/帕拉选择性的策略。从与ArylOBpin（pin =频哪醇盐）的选择性观察，假设部分带负电荷的OBpin基团与催化剂的部分带正电荷的联吡啶配体之间的静电相互作用有利于邻位选择性。通过进一步的计算工作，出现了第二代计算机设计的催化剂，其中用Beg（例如=乙醇酸乙二醇酯）取代Bpin预计可显著提高邻位选择性。实验上，使用B2 eg 2的反应得到邻位选择性> 99%。加入三乙胺显著提高了转化率。这种配体-底物静电相互作用为选择性C-H官能化提供了独特的控制元件。
A strategy for affecting ortho versus meta/para selectivity in Ir-catalyzed C–H borylations (CHBs) of phenols is described. From selectivity observations with ArylOBpin (pin = pinacolate), it is hypothesized that an electrostatic interaction between the partial negatively charged OBpin group and the partial positively charged bipyridine ligand of the catalyst favors ortho selectivity. Experimental and computational studies designed to test this hypothesis support it. From further computational work a second generation, in silico designed catalyst emerged, where replacing Bpin with Beg (eg = ethylene glycolate) was predicted to significantly improve ortho selectivity. Experimentally, reactions employing B2eg2 gave ortho selectivities > 99%. Adding triethylamine significantly improved conversions. This ligand– substrate electrostatic interaction provides a unique control element for selective C–H functionalization.
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