First comprehensive investigation of Suzuki couplings of alkenyl nonaflates with aryl and alkenyl boronic acid derivatives by using classical conditions and microwave heating.
Alkenyl nonaflates (nonafluorobutanesulfonates) are excellent substrates in a variety of palladium-catalysed coupling reactions. We herein demonstrate that bicyclic nonaflates generated from 8-heterobicyclo[3.2.1]octan-3-one derivatives can be coupled with aryl or alkenyl boronic acids in a very efficient manner. The resulting densely functionalised bicyclic skeletons are highly suitable for further synthetic elaboration. The thermal Suzuki couplings provided the expected products in moderate to good yields. Microwave (MW) irradiation dramatically shortened reaction times and gave superior results. Bisboronic ester 19 was also coupled with bicyclic nonaflates, for example, with 14, and double Suzuki-coupling products, such as 22, were isolated in good yields. We demonstrated the great synthetic potential of aryl-substituted 8-heterobicyclo[3.2.1]octene derivatives, such as 15, by the stereoselective conversion of this compound into highly substituted furanose 31 or substituted pyran derivative 33, which were obtained in short and efficient reaction sequences.
Högermeier
Jens
J
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany.
Reissig
Hans-Ulrich
HU
D017738:Alkanesulfonic Acids / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D005466:Fluorocarbons / Q000737:chemistry; D006361:Heating; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D008872:Microwaves; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry
D017738:Alkanesulfonic Acids; D000475:Alkenes; D001897:Boronic Acids; D005466:Fluorocarbons; D006841:Hydrocarbons, Aromatic; D010165:Palladium; C076994:perfluorooctane sulfonic acid