[2.2]Paracyclophane–Triazolyl Monophosphane Ligands: Synthesis and Their Copper and Palladium Complexes

Abstract

Triazole‐based phosphanes have recently been shown to be interesting ligands in organometallic catalysis. The synthesis of novel [2.2]paracyclophane‐substituted triazole‐based phosphane ligands was achieved. The possibility to synthesize these molecules in a highly enantioenriched form is also reported. Moreover, the ability of the novel ligands to coordinate with metal centers was explored. Besides a dinuclear copper complex, a PdII complex could also be isolated, the structure of which was characterized by X‐ray analysis. PdII complexes derived from these ligands provide highly active catalysts for the Suzuki–Miyaura coupling of aryl chlorides.

Regio‐ and Enantioselective Allylation of Phenols via Decarboxylative Allylic Etherification of Allyl Aryl Carbonates Catalyzed by (Cyclopentadienyl)ruthenium(II) Complexes and Pyridine‐Hydrazone Ligands

“…Previously, our group has shown that combinations of [CpRu(CH 3 CN) 3 ][PF 6 ] 1 (10 mol%) and enantiopure pyridine monooxazoline ligands can be efficient for the stereocontrol of such transformations 13d–g. Using pymox L1 in particular, decarboxylative allylic substitution of allyl aryl carbonates gave, for instance, relatively high enantiomeric excesses and regioselectivity (up to 87% ee and b:l>95:5, Scheme ) 13g.…”

“…80% ee ). This is explained by the better leaving group ability of the corresponding nitro‐phenoxide leading to a faster isomerization and racemization 13d. On the other hand, substitutions on the cinnamyl part of electron‐withdrawing groups led to good selectivity levels but lower conversions (entries 6 and 7).…”

Double‐Strand DNA Breaks Induced by Paracyclophane Gold(I) Complexes

“…Thus we assume 1 crystallizes as racemic conglomerate . It is worth noting that due to an efficient methodology for the resolution of racemic formyl[2.2]paracyclophane, the phosphine L1 can be obtained in a highly enantioenriched form, which enables a straightforward synthesis of an enantioenriched gold complex.…”

“…Elemental analyses were carried out with an ElementarVario EL or Micro Cube. [AuCl(tht)], [AuC 6 F 5 (tht)], as well as the employed ligands L1 and L2 and complex 4 were prepared according to literature procedures.…”

“…Also, chiral derivatives are known. Herein, we report the synthesis of different gold complexes of [2.2]paracyclophane‐derived ClickPhos ligands and GemPhos, a [2.2]paracyclophane‐based phosphine . In ClickPhos ligands, a phosphine unit is linked to a paracyclophane scaffold through a triazolyl moiety.…”