Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Nickel‐Catalyzed Synthesis of Pyrimidines via Dehydrogenative Functionalization of Alcohols

Nickel‐Catalyzed Synthesis of Pyrimidines via Dehydrogenative Functionalization of Alcohols Herein we report a comparative study of nickel‐catalyzed syntheses of pyrimidines via dehydrogenative multi‐component coupling of alcohols and amidines using two different classes of nickel catalysts (1 a/1 b and 2 a/2 b) differing with respect to their mode of action during catalysis. The catalysts 1 a and 1 b are two tetracoordinate Ni(II)‐complexes containing two apparently redox‐inactive tetraaza macrocyclic ligands while the catalysts 2 a and 2 b are square planar Ni(II)‐complexes featuring redox‐active diiminosemiquinonato type scaffolds. Catalyst 1 a and 1 b dehydrogenate alcohols via a two‐electron hydride transfer pathway involving energetically demanding nickel‐centered redox events while in the presence of 2 a and 2 b dehydrogenation of alcohols proceeds via a one‐electron hydrogen atom transfer (HAT) pathway via synergistic participation of metal and ligand centered redox processes avoiding high energy nickel centered redox events. Detailed substrate screening and control experiments were performed to unveil the reaction sequence and understand the advantages/disadvantages of these two pathways. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Asian Journal of Organic Chemistry Wiley

Nickel‐Catalyzed Synthesis of Pyrimidines via Dehydrogenative Functionalization of Alcohols

Loading next page...
 
/lp/wiley/nickel-catalyzed-synthesis-of-pyrimidines-via-dehydrogenative-fnoYotPpbs

References (39)

Publisher
Wiley
Copyright
© 2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
2193-5807
eISSN
2193-5815
DOI
10.1002/ajoc.201900695
Publisher site
See Article on Publisher Site

Abstract

Herein we report a comparative study of nickel‐catalyzed syntheses of pyrimidines via dehydrogenative multi‐component coupling of alcohols and amidines using two different classes of nickel catalysts (1 a/1 b and 2 a/2 b) differing with respect to their mode of action during catalysis. The catalysts 1 a and 1 b are two tetracoordinate Ni(II)‐complexes containing two apparently redox‐inactive tetraaza macrocyclic ligands while the catalysts 2 a and 2 b are square planar Ni(II)‐complexes featuring redox‐active diiminosemiquinonato type scaffolds. Catalyst 1 a and 1 b dehydrogenate alcohols via a two‐electron hydride transfer pathway involving energetically demanding nickel‐centered redox events while in the presence of 2 a and 2 b dehydrogenation of alcohols proceeds via a one‐electron hydrogen atom transfer (HAT) pathway via synergistic participation of metal and ligand centered redox processes avoiding high energy nickel centered redox events. Detailed substrate screening and control experiments were performed to unveil the reaction sequence and understand the advantages/disadvantages of these two pathways.

Journal

Asian Journal of Organic ChemistryWiley

Published: Mar 1, 2020

Keywords: ; ; ; ;

There are no references for this article.