Cross-coupling reactions of aromatic and heteroaromatic silanolates with aromatic and heteroaromatic halides.
The alkali-metal salts (potassium and sodium) of a large number of aryl- and heteroarylsilanols undergo efficient cross-coupling with a wide range of aromatic bromides and chlorides under mild conditions to form polysubstituted biaryls. The critical feature for the success of these coupling reactions and their considerable scope is the use of bis(tri-tert-butylphosphine)palladium. Under the optimized conditions, electron-rich, electron-poor, and sterically hindered arylsilanolates afford cross-coupling products in good yields. Many functional groups are compatible with the coupling conditions such as esters, ketones, acetals, ethers, silyl ethers, and dimethylamino groups. Two particularly challenging substrates, (2-benzofuranyl)dimethylsilanolate and (2,6-dichlorophenyl)dimethylsilanolate prepared as their sodium salts showed excellent activity in the coupling reactions, in the former case also with aromatic chlorides. General methods for the efficient synthesis of a wide range of aromatic silanols are also described.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA. sdenmark@illinois.edu
Smith
Russell C
RC
Chang
Wen-Tau T
WT
Muhuhi
Joseck M
JM
D001555:Benzene Derivatives / Q000737:chemistry*; D001713:Biphenyl Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D006846:Hydrocarbons, Halogenated / Q000737:chemistry; D010084:Oxidation-Reduction; D012821:Silanes / Q000737:chemistry*
D001555:Benzene Derivatives; D001713:Biphenyl Compounds; D006846:Hydrocarbons, Halogenated; D012821:Silanes; C082343:silanol