Exploiting Coordination Effects for the Regioselective Zincation of Diazines Using TMPZnX⋅LiX (X=Cl, Br).

Diazines Metalation Regioselectivity Salt Effects Structural Elucidation

Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
04 Oct 2022
Historique:
received: 18 07 2022
pubmed: 10 8 2022
medline: 10 8 2022
entrez: 9 8 2022
Statut: ppublish

Résumé

A new method for regioselective zincations of challenging N-heterocyclic substrates such as pyrimidines and pyridazine was reported using bimetallic bases TMPZnX⋅LiX (TMP=2,2,6,6-tetramethylpiperidyl; X=Cl, Br). Reactions occurred under mild conditions (25-70 °C, using 1.75 equivalents of base without additives), furnishing 2-zincated pyrimidines and 3-zincated pyridazine, which were then trapped with a variety of electrophiles. Contrasting with other s-block metalating systems, which lack selectivity in their reactions even when operating at low temperatures, these mixed Li/Zn bases enabled unprecedented regioselectivities that cannot be replicated by either LiTMP nor Zn(TMP)

Identifiants

pubmed: 35943036
doi: 10.1002/anie.202210491
pmc: PMC9826189
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

e202210491

Subventions

Organisme : Deutsche Forschungsgemeinschaft
Organisme : Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
ID : 188573

Informations de copyright

© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

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Auteurs

Alexander Kremsmair (A)

Department Chemie & Biochemie, Ludwig Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.

Alisa S Sunagatullina (AS)

Department Chemie & Biochemie, Ludwig Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.

Leonie J Bole (LJ)

Department für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012, Bern, Switzerland.

Pasquale Mastropierro (P)

Department für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012, Bern, Switzerland.

Simon Graßl (S)

Department Chemie & Biochemie, Ludwig Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.

Henrik R Wilke (HR)

Department Chemie & Biochemie, Ludwig Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.

Edouard Godineau (E)

Forschung & Entwicklung Stein, Syngenta Crop Protection AG, Schaffhauserstrasse 101, 4332, Stein, Switzerland.

Eva Hevia (E)

Department für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012, Bern, Switzerland.

Paul Knochel (P)

Department Chemie & Biochemie, Ludwig Maximilians-Universität München, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.

Classifications MeSH