A1 Journal article (refereed)
One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ4‐oxo tetranuclear open frame complexes : Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols (2020)

Chinnaraja, E., Arunachalam, R., Pillai, R. S., Peuronen, A., Rissanen, K., & Subramanian, P. S. (2020). One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ4‐oxo tetranuclear open frame complexes : Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols. Applied Organometallic Chemistry, 34(8), Article e5666. https://doi.org/10.1002/aoc.5666

JYU authors or editors

Peuronen, Anssi
Rissanen, Kari

Publication details

All authors or editors: Chinnaraja, E.; Arunachalam, R.; Pillai, R. S.; Peuronen, A.; Rissanen, K.; Subramanian, P. S.

Journal or series: Applied Organometallic Chemistry

ISSN: 0268-2605

eISSN: 1099-0739

Publication year: 2020

Volume: 34

Issue number: 8

Article number: e5666

Publisher: John Wiley & Sons

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1002/aoc.5666

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/73338

Abstract

Synthesis of binuclear Cu(II) terminally closed [2+2]‐ double‐stranded helicate‐like macrocycles 1, 1′,1″, 2, 2′, 2″ and 2+4‐μ4‐oxo tetranuclear open frame complexes 3, 3′, 3″, 4, 4′, 4″ are established. Adapting one‐pot self‐assembly technique from simple three components systems: 1,1′‐binaphthyl‐2,2′‐diamine, 4‐methyl‐2,6‐diformyl phenol and cupric salts, the helicate‐like [2+2]‐ macrocyclic complexes 1–1″, 2–2″ and 2+4‐μ4‐oxo tetranuclear complexes 3–3″, 4–4″ were obtained by appropriately altering the reaction condition such as temperature and subcomponent ratio. Density Functional Theory (DFT) calculations were carried out for understanding the structural geometries, intermediates involved in the diverse formation of [2+2] and 2+4 frameworks. The single crystal X‐ray structures obtained for 1′, 2 and 3 confirms the self‐assembly process in line with DFT. This detailed analysis tempted us to derive a plausible mechanism for this long standing challenge in the synthesis of such macrocycles using 1,1′‐binaphthyl‐2,2′‐diamine (BNDA) and aromatic aldehyde. The chiroptical properties of enantiopure complexes and their catalytic applications in asymmetric oxidative coupling of 2‐naphthol to chiral 1,1’‐Bi‐2‐naphthol (BINOL) achieved in good yield and ee were discussed.

Free keywords: BINOL; helicate; macrocycle; metal template; self‐assembly

Fields of science: