Selective Single-Step Oxidation of Amine to Cross-Azo Compounds with an Unhampered Primary Benzyl Alcohol Functionality

Abstract

This is the first report of a single-step synthesis of primary benzyl alcohol containing different cross-azo compounds (14 examples) by Cu­(II) in the presence of a newly synthesized amino-ether heteroditopic macrobicycle cage. Interestingly, even with extreme conditions, the benzyl alcohol remains unoxidized by the Cu­(II) catalyst due to the protective etherial pocket of the cage.

One‐Pot Dual C−C Coupling Reaction via Site Selective Cascade Formation by PdII‐Cryptate of an Amino‐Ether Heteroditopic Macrobicycle

“…Consequently,t he aryl iodo part of 1a can go throught he site selective Suzuki coupling with arylboronic acid keeping ethynyl iodo part intact from organoborons. To find out the effect of three dimensional macrobicyclic cavity of L1,i ts acyclic analog, [15] L' (Figure 1) has also been explored. Furthermore, to verify the effect of dimension of the macrobicycle cage, an analogousm acrobicycle of L1 having smaller cavity size, L2 (Figure 1, Scheme 1S,S upporting Information) has also been synthesized.…”

“…L1 and L' were synthesized according to the previous literature report. [15] Melting points of all the compounds were determined on aL abtronics digital auto melting/boiling point apparatus. Solution electronic spectra (single and time-dependent) were measured on an Agilent 8453 diode array spectrophotometer.…”

“…Herein, we have studied one-pot dual coupling of ethynyl iodo based aryl iodo substrates throughs ite selectiveS uzuki coupling of aryl iodo center withouth ampering ethynyli odo group, followed by consecutive homocoupling of C(sp) atoms (Scheme 1b). Thiss ite selectivity has been achievedu pon exploring an oxyether-amine based heteroditopic macrobicycle, [15] L1 (Figure 1) as an additive in Pd II catalytic environment. To the best of our knowledge,d riving as ubstrate for ao nepot transformationt hrough selectiveS uzuki coupling on [a] S. Sarkar,Dr.…”

Advances in Application of Azobenzene as a Trigger in Biomedicine: Molecular Design and Spontaneous Assembly

“…In addition, they explored the catalytic and synergistic effects of oxides in the catalyst through DFT calculations and experiments. Ghosh and co‐workers [ 71 ] realized Cu(II)‐catalyzed selective oxidative coupling of aniline using an amino‐ether heteroditopic macrobicycle cage, and they prepared a series of cross‐azo compounds with reliable yield. Based on STM, Venkataraman and co‐workers [ 72 ] developed a single‐molecule selective coupling method for aniline to prepare a series of azobenzenes.…”

Direct Oxidative Azo Coupling of Anilines Using a Self-Assembled Flower-like CuCo2O4 Material as a Catalyst under Aerobic Conditions

“…The conventional methods include diazotization of anilines, reduction of azoxybenzenes, reductive coupling of nitroaromatics, etc . Besides these methods, direct oxidative coupling of anilines using stoichiometric oxidants, such as HgO, /Pb­(OAc) 4 /Mn-based reagents/ t butyl hypoiodite, is also reported. Later, metal-catalyzed azo coupling reactions using O 2 or air as the oxidant have been developed .…”