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Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates.

ABSTRACT: The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C-X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C-O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C-X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2 -1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.

SUBMITTER: Klein P

PROVIDER: S-EPMC6973264 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates.

Klein Philippe P Lechner Vivien Denise VD Schimmel Tanja T Hintermann Lukas L

Chemistry (Weinheim an der Bergstrasse, Germany) 20191126 1

The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C-X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C-O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C-X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl<sub>2</sub> -1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthrol ...[more]

PMID: 31591766

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