Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions

被引：0

作者：

Chattopadhyay, Buddhadeb ^{[1
,3
]}

Dannatt, Jonathan E. ^{[1
]}

Andujar-De Sanctis, Ivonne L. ^{[2
]}

Gore, Kristin A. ^{[1
]}

Maleczka, Robert E. ^{[1
]}

Singleton, Daniel A. ^{[2
]}

Smith, Milton R. ^{[1
]}

机构：

[1] Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing,MI,48824-1322, United States

[2] Department of Chemistry, Texas A and M University, PO Box 30012, College Station,TX,77842, United States

[3] Center of Bio-Medical Research, Division of Molecular Synthesis and Drug Discovery, Sanjay Gandhi Post Graduate Institute of Medical Sciences, Raebareli Road, Lucknow, Uttar Pradesh,226014, India

来源：

Journal of the American Chemical Society | 2017年 / 139卷 / 23期

关键词：

Coulomb interactions - Ethylene - Catalysis - Catalyst selectivity - Complexation - Ligands;

D O I：

暂无

中图分类号：

学科分类号：

摘要：

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. © 2017 American Chemical Society.

引用

页码：7864 / 7871

共 1 条

[1] Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions
Chattopadhyay, Buddhadeb
Dannatt, Jonathan E.
Andujar-De Sanctis, Ivonne L.
Gore, Kristin A.
Maleczka, Robert E., Jr.
Singleton, Daniel A.
Smith, Milton R., III
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (23) : 7864 - 7871

← 1 →