Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from the Cu(ii)-mediated direct trifluoromethylthiolation reaction of arenes via reactive arylcopper(iii) intermediates

Abstract

Using azacalix[1]arene[3]pyridines and their high valent organocopper(II) and (III) complexes as probes, arene C-H bond trifluoromethylthiolation was investigated. While arylcopper(II) compounds appeared almost inert, arylcopper(III) compounds reacted efficiently with a nucleophilic trifluoromethylthiolating reagent. Under mild conditions, azacalix[1]arene[3]pyridines underwent the regioselective Cu(ClO 4 ) 2mediated one-pot trifluoromethylthiolation reaction with Me 4 NSCF 3 to afford low-rim functionalized macrocycles. † Electronic supplementary information (ESI) available: 1 H and 13 C NMR spectra of all products, and X-ray structures of 6a, 7b and 7c (CIFs). CCDC 1474334-1474336. For ESI and crystallographic data in CIF or other electronic format see

Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide

“…4‐( tert ‐Butyl)‐1‐methyl‐2‐[(trifluoromethyl)sulfinyl]benzene (3d′): Colorless liquid. 54 % (14.2 mg).…”

Significant Difference in Semiconducting Properties of Isomeric All‐Acceptor Polymers Synthesized via Direct Arylation Polycondensation

“…The obtained polymers showed no homocoupling defects and relatively good molecular weights (up to 10 kg mol −1 ) . Recent studies revealed that the Cu‐catalyzed C−H activation reactions proceed through organometallic C‐Cu intermediates –. In the mechanism of Pd‐catalyzed direct arylation, the Cu species have two roles.…”

Azacalixquinarenes: From Canonical to (Poly-)Zwitterionic Macrocycles

“…5 Since seminal works in the late nineties on polyazacalixarenes, [6][7][8][9][10] this family has been growing to incorporate trypticene moieties, 11,12 pyridine units, 13,14 and covalently-bonded metallic centers conferring unusual reactivity. [15][16][17][18][19][20] Noteworthy, ACA macrocycles were valorized for carbon dioxide uptake, 21,22 fullerene or anions complexation [23][24][25] and demonstrated to be relevant as hole-and spin-containing architectures. 26,27 In 2013, the azacalixphyrin (ACP, Figure 1) was reported as the only known "azacalixarene-like" derivative introducing four oxidized tetraaminobenzene units that promote a stable bis-zwitterionic ground electronic state.…”

“…Heteroatom-bridged calixarenes are an evolved class of calixarene macrocycles , in which the introduction of a bridging heteroatom in lieu of a methylene link provides additional features such as (i) the tuning of the cavity size and of the conformation (e.g., 1,3-alternate structure), (ii) new redox properties, and (iii) conjugation between the units of the macrocyclic oligomer. , Beyond the wide range of heteroatom-containing calixarenes developed during the past decades, azacalixarenes (ACA) demonstrated an undeniable versatility regarding structure–property shaping . Since seminal works in the late 1990s on polyazacalixarenes, − this family has been growing to incorporate trypticene moieties, , pyridine units, , and covalently bonded metallic centers conferring unusual reactivity. − Noteworthy, ACA macrocycles were valorized for carbon dioxide uptake , and fullerene or anion complexation − and demonstrated to be relevant as hole- and spin-containing architectures. , In 2013, the azacalixphyrin (ACP, Figure ) was reported as the only known “azacalixarene-like” derivative introducing four oxidized tetraaminobenzene units that promote a stable bis-zwitterionic ground electronic state. − Consequently, ACP can be viewed as a masked conjugated azacalixquinone. Its aromatic core involving 18 π-electrons confers to the ACP a strong absorption at ca.…”