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

被引：135

作者：

Chattopadhyay, Buddhadeb ^{[1
,3
]}

Dannatt, Jonathan E. ^{[1
]}

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

Gore, Kristin A. ^{[1
]}

Maleczka, Robert E., Jr. ^{[1
]}

Singleton, Daniel A. ^{[2
]}

Smith, Milton R., III ^{[1
]}

机构：

[1] Michigan State Univ, Dept Chem, 578 South Shaw Lane, E Lansing, MI 48824 USA

[2] Texas A&M Univ, Dept Chem, POB 30012, College Stn, TX 77842 USA

[3] Sanjay Gandhi Post Grad Inst Med Sci, Div Mol Synth & Drug Discovery, Ctr Biomed Res, Raebareli Rd, Lucknow 226014, Uttar Pradesh, India

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 23期

关键词：

C-H BORYLATION; TRANSITION-METAL CATALYSIS; MOLECULAR RECOGNITION; BORON HETEROCYCLES; SUPRAMOLECULAR CONTROL; SELECTIVITY; ARENES; FUNCTIONALIZATION; REGIOSELECTIVITY; DERIVATIVES;

D O I：

10.1021/jacs.7b02232

中图分类号：

O6 [化学];

学科分类号：

0703 ;

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-7 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. Experinientally, reactions employing B(2)eg(2) gave ortho selectivities > 99%. Adding triethylamine significantly improved conversions. This ligand-substrate electrostatic interaction provides a unique control element for selective C-H functionalization.

引用

页码：7864 / 7871

页数：8

共 55 条

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