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An Improved Method for the Bromination of Metalated Haloarenes via Lithium, Zinc Transmetalation: A Convenient Synthesis of 1,2-Dibromoarenes

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Karsten Menzel,*^† Ethan L. Fisher,^† Lisa DiMichele,^‡ Doug E. Frantz,^† Todd D. Nelson,^† and Michael H. Kress^†

Merck Research Laboratories, Department of Process Research, Merck & Co., Inc., 466 Devon Park Drive, Wayne, Pennsylvania 19087, and Merck Research Laboratories, Department of Process Research, Merck & Co., Inc., 126 E. Lincoln Avenue, Rahway, New Jersey 07065 %karsten_menzel@merck.com

J. Org. Chem., 2006, 71 (5), pp 2188–2191

DOI: 10.1021/jo052515k

Publication Date (Web): February 8, 2006

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Merck & Co., Inc., Wayne, Pennsylvania.

‡

Merck & Co., Inc., Rahway, New Jersey.

Abstract

A facile protocol for the synthesis of 1,2-dibromoarenes is described. A standard ortho-lithiation/bromination procedure, when applied to bromoarenes, resulted in poor yields of the corresponding 1,2-dibromoarenes (13−62% yield). However, transmetalation of the transient aryllithium intermediate to an arylzinc species with ZnCl₂, followed by bromination, resulted in dramatically improved yields of the synthetically useful 1,2-dibromoarenes (68−95% yield).

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Published In Issue March 03, 2006
Received December 6, 2005

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An Improved Method for the Bromination of Metalated Haloarenes via Lithium, Zinc Transmetalation: A Convenient Synthesis of 1,2-Dibromoarenes