Substituted Benzenes: The Kirsch Synthesis of Cybrodol

Abstract

Stephen L. Buchwald of MIT established (J. Am. Chem. Soc. 2010, 132, 14076) a Pd-catalyzed protocol for conversion of an aryl triflate 1 to the halide 2. Jie Wu of Fudan University prepared (Tetrahedron Lett. 2010, 51, 6646) aromatic halides from the corresponding carboxylic acids. Yong-Chua Teo of Nanyang Technological University described (Tetrahedron Lett . 2010, 51, 3910) the Mn-mediated conversion of 3 to 5, suggesting a benzyne intermediate. Takanori Shibata of Waseda University effected (Synlett 2010, 2601) the direct Ru-mediated coupling of aryl halides with amines, and Paul Helquist of the University of Notre Dame prepared (J. Org. Chem. 2010, 75, 4887) anilines by coupling aryl halides with NaN3 . Chao-Jun Li of McGill University devised (Tetrahedron Lett. 2010, 51, 5486) the Pd-catalyzed decarbonylative Heck coupling of 6 with 7 to give 8. Mats Larhed of Uppsala University showed (Angew. Chem. Int. Ed. 2010, 49, 7733) that Pd could also catalyze the decarboxylative coupling of an aromatic acid 9 with a nitrile to give the ketone 10. Dennis G. Hall of the University of Alberta found (Tetrahedron Lett. 2010, 51, 4256) that an areneboronic acid could promote the Zr-catalyzed ortho condensation of a phenol 11 with an aldehyde, leading to 12, which could then be carried on to a range of other products. Professor Hall also showed (Angew. Chem. Int. Ed. 2010, 49, 2883) that areneboronic acids are stable to many standard organic transformations, and that the product boronic acids can be readily purified by extraction into sorbitol/Na2CO3. Professor Buchwald reported (J. Am. Chem. Soc. 2010, 132, 14073) an optimized source of Pd for the Suzuki-Miyaura coupling, allowing the room-temperature participation even of unstable boronic acids such as 13. Wing-Yiu Yu of the Hong Kong Polytechnic University observed (J. Am. Chem. Soc. 2010, 132, 12862) that 17 was an effective donor for the Pd-catalyzed ortho C-H amination of 16. Nicholas C. O. Tomkinson of Cardiff University uncovered (Synlett 2010, 2471) the facile rearrangement of 19 to 20. Professor Buchwald described (J. Am. Chem. Soc. 2010, 132, 9990) the coupling of 21, prepared from the aryl halide, with 22 to give the benzofuran 23.