Scope and Limitations of the Liebeskind–Srogl Cross-Coupling Reactions Involving the Biellmann BODIPY

Abstract

Several new examples of meso-(het)arylBODIPY were prepared via the Liebeskind-Srogl (L-S) cross-coupling reaction of the Biellmann BODIPYs (1a,b) and aryl- and heteroarylboronic acids in good to excellent yield. It was shown that this reaction could be carried out under microwave heating to shorten reaction times and/or increase the yield. It was illustrated that organostannanes also participate in the L-S reaction to give the corresponding BODIPY analogues in short reaction times and also with good to excellent yields. We analyze the role of the substituent at the sensitive meso position in the photophysical signatures of these compounds. In particular, the rotational motion of the aryl ring and the electron donor ability of the anchored moieties rule the nonradiative pathways and, hence, have a deep impact in the fluorescence efficiency.

Development of Lysosome‐Targeted Fluorescent Probes for Cys by Regulating the Boron‐dipyrromethene (BODIPY) Molecular Structure

“…Considering that reactive oxygen species (ROS)/reactive nitrogen species (RNS) species may potentially oxidize thioethers, [57][58][59][60][61][62] the interference of ROS/RNS in the detectiono fC ys was also evaluated and the results are collectedi nF igure S11 (in the Supporting Information). It can be clearly seen that the detection of Cys with our probes (Lyso-S and Lyso-D)w as not affected by ROS/RNSs pecies.…”

Indolylboronic Acids: Preparation and Applications

“…Interestingly, the cross-coupling reaction was achieved by means of a catalytic amount of the Rh catalyst [165]. The Liebeskind−Srogl cross-coupling reaction was used for the synthesis of substituted BODIPY involving Biellmann BODIPY (Table 10, entry 2) [166]. The reaction was catalyzed by Pd 2 (dba) 3 in the presence of a catalytic amount of trifurylphosphine and a stoichiometric amount of CuTC, thereby leading to variously substituted BODIPYs.…”

Functionalized boron-dipyrromethenes and their applications

“…30 In the subsequent steps, the thioketone was reacted with CH 3 I followed by treatment with tertiary amine and complexation with BF 3 ⋅ OEt 2 to produce 8-thiomethyl BODIPY 3. Peña-Cabrera et al [32][33][34][35][36][37] used 8-thiomethyl BODIPY 3 to prepare a series of mesosubstituted BODIPYs under Liebeskind-Srogl cross-coupling reaction conditions. 31 The 8-thiomethyl BODIPY 3 was treated with aryl, heteroaryl, alkenyl and organometallic boronic acids ( Figure 4) in the presence of a catalytic amount of Pd(0)/trifurylphosphine and a stoichiometric amount of Cu(I)-2-thienylcarboxylate under neutral conditions and prepared corresponding meso-substituted BODIPYs 4-9.…”

“…31 The 8-thiomethyl BODIPY 3 was treated with aryl, heteroaryl, alkenyl and organometallic boronic acids ( Figure 4) in the presence of a catalytic amount of Pd(0)/trifurylphosphine and a stoichiometric amount of Cu(I)-2-thienylcarboxylate under neutral conditions and prepared corresponding meso-substituted BODIPYs 4-9. [32][33][34][35][36][37] The reaction also works efficiently if one uses organostannanes instead of boronic acids under the same Pd(0) coupling conditions. 38 They have used this methodology to prepare different types of meso-aryl functionalized BODIPYs like 10 and the functionalized meso-aryl group was used as handle for additional elaboration.…”