Acceptorless Dehydrogenative Synthesis of Pyrimidines from Alcohols and Amidines Catalyzed by Supported Platinum Nanoparticles

• Published in: ACS catalysis 2018-12, Vol.8 (12), p.11330-11341
• Main Authors: Sultana Poly, Sharmin, Siddiki, S. M. A. Hakim, Touchy, Abeda S, Ting, Kah Wei, Toyao, Takashi, Maeno, Zen, Kanda, Yasuharu, Shimizu, Ken-ichi
• Format: Article
• Language: English
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.8b02814

A one-pot, acceptorless dehydrogenative method, using a carbon-supported Pt catalyst (Pt/C) along with KOtBu, has been developed for the synthesis of 2,4,6-trisubstituted pyrimidines from secondary and primary alcohols, and amidines. The reaction takes place efficiently using a wide range of substrate scopes (32 examples with isolated yields up to 92%). The Pt/C catalyst that promotes this process is reusable and has a higher turnover number (TON) than those employed in previously reported methods. The results of mechanistic studies suggest that the process takes place through a pathway that begins with Pt-catalyzed acceptorless dehydrogenation of the alcohol substrate, which is followed by sequential condensation, cyclization, and dehydrogenation. Measurements of the turnover frequency combined with the results of density functional theory calculations on different metal surfaces suggest that the adsorption energy of H on the Pt surface is optimal for the acceptorless dehydrogenation process, which causes the higher catalytic activity of Pt over those of other metals.