Reagent Control Enables Selective and Regiodivergent Opening of Unsymmetrical Phenonium Ions

Shiyan Xu; Hannah M. Holst; Shelby B. McGuire; Nicholas J. Race

doi:10.1021/jacs.0c02095

Reagent Control Enables Selective and Regiodivergent Opening of Unsymmetrical Phenonium Ions

Shiyan Xu, Hannah M. Holst, Shelby B. McGuire, Nicholas J. Race

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

We report the first examples of selective and regiodivergent opening of unsymmetrical phenonium ions with chloride ions. These reactions are enabled by the dual role of SnCl₄ and TiCl₄ as Lewis acids and chloride nucleophiles. Reagent control dictates addition of chloride at either the substituted internal position (SnCl₄) or unsubstituted terminal position (TiCl₄) of the phenonium ion. These reactions are highly selective, stereospecific, operationally simple, and proceed in good to excellent yields. Diverse product utility is demonstrated.

Original language	English (US)
Pages (from-to)	8090-8096
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	142
Issue number	18
DOIs	https://doi.org/10.1021/jacs.0c02095
State	Published - May 6 2020

Bibliographical note

Funding Information:
This work was funded by the University of Minnesota and the American Chemical Society Petroleum Research Fund (PRF 60782-DNI1). We thank Professors Topczewski, Tonks, and Roberts (UMN) for insightful discussions. The Topczewski lab is thanked for supplying chemicals and assistance with SFC/HPLC analysis. We thank Dr. Victor G. Young, Jr., and the X-ray Crystallographic Laboratory at the University of Minnesota for crystallographic analysis of 6z , 7c , and 9ac .

Publisher Copyright:
© 2020 American Chemical Society.

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abstract = "We report the first examples of selective and regiodivergent opening of unsymmetrical phenonium ions with chloride ions. These reactions are enabled by the dual role of SnCl4 and TiCl4 as Lewis acids and chloride nucleophiles. Reagent control dictates addition of chloride at either the substituted internal position (SnCl4) or unsubstituted terminal position (TiCl4) of the phenonium ion. These reactions are highly selective, stereospecific, operationally simple, and proceed in good to excellent yields. Diverse product utility is demonstrated.",

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AU - McGuire, Shelby B.

AU - Race, Nicholas J.

N1 - Funding Information: This work was funded by the University of Minnesota and the American Chemical Society Petroleum Research Fund (PRF 60782-DNI1). We thank Professors Topczewski, Tonks, and Roberts (UMN) for insightful discussions. The Topczewski lab is thanked for supplying chemicals and assistance with SFC/HPLC analysis. We thank Dr. Victor G. Young, Jr., and the X-ray Crystallographic Laboratory at the University of Minnesota for crystallographic analysis of 6z , 7c , and 9ac . Publisher Copyright: © 2020 American Chemical Society.

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N2 - We report the first examples of selective and regiodivergent opening of unsymmetrical phenonium ions with chloride ions. These reactions are enabled by the dual role of SnCl4 and TiCl4 as Lewis acids and chloride nucleophiles. Reagent control dictates addition of chloride at either the substituted internal position (SnCl4) or unsubstituted terminal position (TiCl4) of the phenonium ion. These reactions are highly selective, stereospecific, operationally simple, and proceed in good to excellent yields. Diverse product utility is demonstrated.

AB - We report the first examples of selective and regiodivergent opening of unsymmetrical phenonium ions with chloride ions. These reactions are enabled by the dual role of SnCl4 and TiCl4 as Lewis acids and chloride nucleophiles. Reagent control dictates addition of chloride at either the substituted internal position (SnCl4) or unsubstituted terminal position (TiCl4) of the phenonium ion. These reactions are highly selective, stereospecific, operationally simple, and proceed in good to excellent yields. Diverse product utility is demonstrated.

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Reagent Control Enables Selective and Regiodivergent Opening of Unsymmetrical Phenonium Ions

Abstract

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