The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

Abstract

The Pd-catalyzed, Cu I Àcarboxylate-mediated crosscoupling reactiono fo rganosulfur compounds with nucleophilic organometallic reagents is knowna st he Liebeskind-Srogl cross-coupling reaction. Owing to the readily available starting materials and neutral reactionc onditions, it has become an attractive procedure for the formation of carbonÀcarbon bonds, in particularf or cases in whicht radi-tional methods had failed. Since the seminal work of Liebeskind and Srogl in 2000, this reactionh as received intense attentionf rom the synthetic community.I nt his Focus Review,w eh ighlight recent advances in this intriguing cross-coupling reactiona nd its applications in organic synthesis.Scheme1.Liebeskind-Srogl cross-coupling reaction.Scheme2.The original Liebeskind-Sroglc ross-coupling reaction.d ba = dibenzylideneacetone, TFP = tri-2-furanylphosphine [a] Dr.Scheme4.Cross-coupling reaction between a-amino acid thiol esters and organostannanes. Cbz = benzyloxycarbonyl.Scheme5.Cross-coupling reaction between thiol esters and B-alkyl-9-BBN. 9-BBN = 9-borabicyclo[3.3.1]nonane.Scheme6.One-pothydroboration/intramolecular-cross-couplingr eaction between thiol esters and B-alkyl-9-BBN. DIPEA = N,N-diisopropylethylamine.Scheme7.Cross-coupling reaction between thiol esters andorganoindium reagents.Scheme8.Cross-coupling reaction between thiol esters andorganosilicon reagents. TBAF = tetra-n-butylammonium fluoride.Scheme9.Intramolecular cross-coupling reaction between thiol esters and olefins.Scheme38. Cross-coupling reaction between diaryld isulfides and boronicacids/terminal-alkynes.Scheme55. Synthesis of the C 15 ÀC 36 segment of goniodomin A. TBS = tert-butyldimethylsilyl, TBDPS = tert-butyldiphenylsilyl.Scheme56. To talsynthesis of verbenachalcone. MOM = methoxymethyl.Scheme57. Synthesis of enigmol and its stereoisomers. Boc = tert-butyloxycarbonyl.Scheme58. To talsynthesis of (À)-agelastatins A-F.Scheme59. Synthesis of quinone-containing salvinorin Aa nalogues.Scheme60. Synthesis of Soai-type aldehydes.

Ready Access to Molecular Rotors Based on Boron Dipyrromethene Dyes-Coumarin Dyads Featuring Broadband Absorption

“…Salicyladehyde was attached to BODIPY via the Liebeskind-Srogl cross-coupling (LSCC) reaction [31] between commercially available 8-methylthioBODIPY 1 and boronic acid 2 (Scheme 1). From the synthetic point of view, the utilization of salicylaldehyde as a versatile building block is well-documented [27].…”

“…Salicyladehyde was attached to BODIPY via the Liebeskind-Srogl cross-coupling (LSCC) reaction [31] between commercially available 8-methylthioBODIPY 1 and boronic acid 2 (Scheme 1). Despite the fact that coumarin-BODIPY hybrids are known, and some examples of these dyads can be found in the literature applied as chemosensors [20,21], energy transfer cassettes [22,23] or fluorescent probes for bioimaging [24,25], the photonic performance, and hence the practical applicability of these multifunctional molecular assemblies, can be still improved.…”

“…Salicyladehyde was attached to BODIPY via the Liebeskind-Srogl cross-coupling (LSCC) reaction [31] between commercially available 8-methylthioBODIPY 1 and boronic acid 2 (Scheme 1).…”

Microwave-Assisted Palladium-Catalyzed Cross-Coupling Reactions: Generation of Carbon–Carbon Bond

“…The Liebeskind-Srogl reaction was recently developed in 2000 [111]. It represents a powerful method developed lately for the construction of C-C bonds through the palladium-catalyzed cross-coupling of thio-organic compounds with various electrophilic reagents, such as boronic acids and organostannanes, in the presence of stoichiometric amount of copper salt [112,113].…”

Biocompatible metal-assisted C–C cross-coupling combined with biocatalytic chiral reductions in a concurrent tandem cascade

“…In 2000, Liebeskind and Srogl (L-S) published a copper mediated, palladium catalyzed C-C cross-coupling protocol of thioesters (TEs) with boronic acids for the formation of ketones under aerobic conditions (Scheme 1). [21][22][23] The method was later successfully extended to aryl coupling reactions based on the orthogonal behavior of the S-alkyl leaving group. 24 This coupling reaction operates at neutral pH (base free conditions), in organic solvents (e.g., THF) and with a phosphite additive, activating the catalyst to work at room temperature.…”