Simple, General, and Efficient Synthesis of Meso-Substituted Borondipyrromethenes from a Single Platform

Abstract

An unprecedented synthesis of 8-substituted-borondipyrromethenes is described starting from 8-thiomethylbodipy 1. Aryl, heteroaryl, alkenyl, and organometallic boronic acids smoothly reacted with 1 in the presence of a catalytic amount of Pd(0) and a stoichiometric amount of Cu(I)-2-thienylcarboxylate under neutral conditions to give the corresponding Bodipy analogues in good to quantitative yields (20 examples). A remarkable reactivity was observed in some cases, e.g., ferrocenylboronic acid gave the product in 98% isolated yield after only 10 min at 55 degrees C.

The inorganic DMSO/POCl3 reaction with BODIPY: wide product formation and implications for biological ROS sensing and neurodegenerative disease research

“…Reports of 3-thienyl [4,[13][14][15][16]] and 3-furyl groups are fewer [13]. 2-furyl reports often coincide with those for 2-thienyl [5,12,13,17,18]. Sulfide substitutions can become chemically oxidized species and give rise to discrete valence state increases; subsequent fluorescence or colorimetric changes may ensue.…”

“…With simple heteroatom placement and rotor changes, new photomolecular tools can emerge. Heteroatom diversity has extended to the 8-aryl group: 8-furyl and 8-thienyl systems were first reported in 2007 [4,5]. 8-position multithienyl conjugates [6][7][8][9], aniline-containing extensions [10,11], and fluorophore extensions have also led to BODIPY versatility [12].…”

Thiocyanation of BODIPY dyes and their conversion to thioalkylated derivatives

“…5 To the best of our knowledge, thiocyanatosubstituted boron dipyrrins have not been previously reported, although they can be considered starting materials for BODIPY sulfides. [6][7][8][9][10] For this study, ten BODIPYs (Table 1) were synthesized using established procedures [11][12][13][14][15][16][17][18] and were used as starting materials for further reactions. …”

Photofunctional Conductors Based on TTF‐BODIPY Dyads Bearing p‐Phenylene and p‐Phenylenevinylene Spacers

“…Tributylstannyl‐substituted TTF derivatives 3a – c were synthesized from three TTF derivatives, TTF, ethylenedithio‐TTF (EDT‐TTF) and EDO‐TTF, following the reported conventional methods 13,14. Then, Stille coupling reactions between the TTF derivatives 3a – c and p ‐bromophenyl‐BODIPY ( 4 )15 were performed in toluene at reflux by using [Pd(PPh 3 ) 2 Cl 2 ] as catalyst to obtain TTF‐BODIPY dyads 1a – c with a p ‐phenylene spacer in yields of 52, 22 and 35 %, respectively. On the other hand, the Wittig reagent phenyl‐BODIPY 6 was prepared by the reaction of p ‐(bromomethyl)phenyl‐BODIPY ( 5 )15,16 with triphenylphosphine in benzene at reflux.…”