Organic Chemistry Portal
Organic Chemistry Highlights

Monday, September 26, 2011
Douglass F. Taber
University of Delaware

Functionalization and Homologation of C-H Bonds

Justin Du Bois of Stanford University developed (J. Am. Chem. Soc. 2010, 132, 10202. DOI: 10.1021/ja1046999) a Ru catalyst for the stereoretentive hydroxylation of 1 to 2. John T. Groves of Princeton University effected (J. Am. Chem. Soc. 2010, 132, 12847. DOI: 10.1021/ja105548x) equatorial chlorination of the test substrate 3. Kenneth M. Nicholas of the University of Oklahoma found (J. Org. Chem. 2010, 75, 7644. DOI: 10.1021/jo1015213) that I2 catalyzed the amination of 5. Thorsten Bach of the Technische Universität München established (Org. Lett. 2010, 12, 3690. DOI: 10.1021/ol101517v) that the amination of 7 proceeded with significant diastereoselectivity. Phil S. Baran of Scripps/La Jolla compiled (Synlett 2010, 1733. DOI: 10.1055/s-0030-1258123) an overview of the development of C-H oxidation.

Tethering can improve the selectivity of C-H functionalization. X. Peter Zhang of the University of South Florida devised (Angew. Chem. Int. Ed. 2010, 49, 10192. DOI: 10.1002/anie.201005552) a Co catalyst for the cyclization of 9 to 10. Teck-Peng Loh of Nanyang Technological University established (Angew. Chem. Int. Ed. 2010, 49, 8417. DOI: 10.1002/anie.201003646) conditions for the aerobic oxidation of 11 to 12.

Jin-Quan Yu, also of Scripps/La Jolla, effected (J. Am. Chem. Soc. 2010, 132, 17378. DOI: 10.1021/ja108754f) carbonylation of methyl C-H of 13, to give 14. Sunggak Kim, now also at Nanyang Technological University, established (Synlett 2010, 1647. DOI: 10.1055/s-0029-1219960) conditions for the free-radical homologation of 15 to 17. Gong Chen of Pennsylvania State University extended (Org. Lett. 2010, 12, 3414. DOI: 10.1021/ol101220x) his work on remote Pd-mediated activation by cyclizing 18 to 19.

Many schemes have been developed in recent years for the oxidation of substrates to reactive electrophiles. Gonghua Song of the East China University of Science and Technology and Chao-Jun Li of McGill University reported (Synlett 2010, 2002. DOI: 10.1055/s-0030-1258128) Fe nanoparticles for the oxidative coupling of 20 with 21. Zhi-Zhen Huang of Nanjing University found (Org. Lett. 2010, 12, 5214. DOI: 10.1021/ol102252n) that protonated pyrrolidine 25 was important for mediating the site-selective coupling of 24 with 23. Y. Venkateswarlu of the Indian Institute of Chemical Technology, Hyderabad, was even able (Tetrahedron Lett. 2010, 51, 4898. DOI: 10.1016/j.tetlet.2010.07.080) to effect coupling with a cyclic alkene 28.

AB3217-A (32), isolated in 1992, was shown to have marked activity against two spotted spider mites. Christopher R. A. Godfrey of Syngenta Crop Protection, Münchwilen prepared (Synlett 2010, 2721. DOI: 10.1055/s-0030-1259010) 32 from commercial anisomycin 30a. The key step in the synthesis was the oxidative cyclization of 30b to 31.

D. F. Taber, Org. Chem. Highlights 2011, September 26.