Synlett
DOI: 10.1055/s-0036-1588837
letter
© Georg Thieme Verlag Stuttgart · New York

Selective Zincation of 1,2-Dicyanobenzene and Related Benzonitriles in Continuous Flow Using In Situ Trapping Metalations

Marthe Ketels ‡, Dorothée S. Ziegler ‡, Paul Knochel*
  • Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Haus F, 81377 München, Germany   Email: paul.knochel@cup.uni-muenchen.de
Further Information

Publication History

Received: 10 April 2017

Accepted after revision: 26 April 2017

Publication Date:
06 June 2017 (eFirst)

Dedicated to Professor Victor Snieckus on the occasion of his 80th birthday and in recognition of his pioneer contributions in organometallic chemistry

These authors contributed equally.

Abstract

A mild and general metalation procedure for the functionalization of 1,2-dicyanobenzene and related polyfunctionalized benzonitriles using a commercially available continuous flow setup is reported. The addition of TMPLi (TMP = 2,2,6,6-tetramethylpiperidyl) to a mixture of an aromatic substrate with a metallic salt such as ZnCl2 under appropriate conditions (0 °C, 20 s) leads to fast in situ lithiation of the arene followed by transmetalation with ZnCl2 to afford the corresponding functionalized arylzinc compound that were trapped with various electrophiles in high yields. The reaction scope of these in situ trapping metalations in flow is broader and needs less equivalents of the base and the metal salt than the corresponding batch procedure.

Supporting Information