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

Fusun Seyma Gungor*, B. Sebnem Sesalan, Nurcan Senyurt Tuzun, Yilmaz Ozkilic, Olcay Anac

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

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 α-ionone and the [3 + 2] carbonyl-ylide reaction of dimethyl diazomalonate with thiophene-2-carbaldehyde 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.

Original languageEnglish
Article number131892
JournalTetrahedron
Volume80
DOIs
Publication statusPublished - 29 Jan 2021

Bibliographical note

Publisher Copyright:
© 2020 Elsevier Ltd

Funding

Istanbul Technical University Scientific Research Fund supported this work (Project No: 39424 ). The authors acknowledge the National High Performance Computing Centre at ITU (grant no. 5004722017 ) for computational sources.

FundersFunder number
National High Performance Computing Centre
International Technological University5004722017

    Keywords

    • Carbene
    • Cycloaddition
    • DFT
    • Metallophthalocyanine
    • Ylide

    Fingerprint

    Dive into the research topics of 'Non-peripherally substituted metallophthalocyanines catalyzed diastereoselective carbonyl-ylide reactions: Synthesis and DFT calculations'. Together they form a unique fingerprint.

    Cite this