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One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ 4 ‐oxo tetranuclear open frame complexes: Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols
Author(s) -
Chinnaraja Eswaran,
Arunachalam Rajendran,
Pillai Renjith S.,
Peuronen Anssi,
Rissanen Kari,
Subramanian Palani S.
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5666
Subject(s) - chemistry , enantiopure drug , diamine , yield (engineering) , oxidative coupling of methane , aldehyde , density functional theory , catalysis , enantioselective synthesis , stereochemistry , phenol , chirality (physics) , crystallography , combinatorial chemistry , computational chemistry , polymer chemistry , organic chemistry , materials science , metallurgy , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model
Synthesis of binuclear Cu(II) terminally closed [ 2+2 ]‐ double‐stranded helicate‐like macrocycles 1, 1′ , 1″ , 2 , 2′ , 2″ and 2+4‐ μ 4 ‐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‐ μ 4 ‐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.