Non-peripherally substituted metallophthalocyanines catalyzed diastereoselective carbonyl-ylide reactions: Synthesis and DFT calculations

Güngör F. Ş., Sesalan B. Ş., Tüzün N., Özkılıç Y., Anaç O.

TETRAHEDRON, cilt.80, 2021 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 80
  • Basım Tarihi: 2021
  • Doi Numarası: 10.1016/j.tet.2020.131892
  • Dergi Adı: TETRAHEDRON
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Aquatic Science & Fisheries Abstracts (ASFA), BIOSIS, Biotechnology Research Abstracts, CAB Abstracts, Chemical Abstracts Core, Chimica, EMBASE, Veterinary Science Database
  • İstanbul Teknik Üniversitesi Adresli: Evet

Özet

Many catalysts are used to control the chemo-selectivity, diastereoselectivity, and enantioselectivity in carbenoid reactions. In this work, the [4 + 1] carbonyl-ylide reaction of dimethyl diazomalonate with ccionone and the [3 + 2] carbonyl-ylide reaction of dimethyl diazomalonate with thiophene-2carbaldehyde were chosen to obtain enriched diastereomeric products with the synthesized metallophthalocyanine compounds as catalysts. Four metallophthalocyanines (MPcs) including two neopenthoxy substituted and two novel fenchoxy substituted on non-peripheral positions of phthalocyanine ring were synthesized. Their catalytic activities were also compared with several common catalysts. Our results showed that in both reactions copper-Pc with neopentyl is the most effective catalyst to obtain diastereoselective results with diastereomeric product ratios of 30:70 and 10:90. DFT calculations also performed to explain the effect of the catalyst in diastereoselectivity. The calculations were in good agreement with the experimental results and assisted in understanding the selectivity. (C) 2020 Elsevier Ltd. All rights reserved.