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Monday, September 19, 2011
Douglass F. Taber
University of Delaware

Functionalization and Homologation of Alkenes

Masahito Ochiai developed (Reduction, Oxidation and Homologation of Alkenes 2008, March 24) the iodosobenzene-mediated cleavage of alkenes to keto aldehydes. Thottumkara K. Vinod of Western Illinois University described (Org. Lett. 2010, 12, 5640. DOI: 10.1021/ol1023807) a modified protocol that delivered the keto acid 2. Chi-Ming Che of the University of Hong Kong established (J. Am. Chem. Soc. 2010, 132, 13229. DOI: 10.1021/ja100967g) a method for the preparative scale Fe-catalyzed cis dihydroxylation of an alkene 3. Ilhyong Ryu of Osaka Prefecture University devised (Synlett 2010, 2014. DOI: 10.1055/s-0030-1258482) a practical procedure for the free radical addition of HBr to an alkene 5. Tetsuo Ohta of Doshisha University showed (Tetrahedron Lett. 2010, 51, 2806. DOI: 10.1016/j.tetlet.2010.03.052) that a Ru catalyst could add an aromatic acid to the internal carbon of a terminal alkene 7.

Noriki Kutsumura and Takao Saito of the Tokyo University of Science found (Org. Lett. 2010, 12, 3316. DOI: 10.1021/ol101110v) conditions for bromination/dehydrobromination to convert 10 to 11. Tsuyoshi Taniguchi of Kanazawa University oxidized (J. Org. Chem. 2010, 75, 8126. DOI: 10.1021/jo101769d) the alkene 12 to the nitro alkene 13.

Professor Taniguchi added (Angew. Chem. Int. Ed. 2010, 49, 10154. DOI: 10.1002/anie.201005574) methyl carbazate to 14 to give the β-hydroxy ester 15. Philippe Renaud of the University of Bern effected (J. Am. Chem. Soc. 2010, 132, 17511. DOI: 10.1021/ja1068036) the free radical homologation of 16 to the azide 18. Daniel P. Becker of Loyola University described (Tetrahedron Lett. 2010, 51, 3514. DOI: 10.1016/j.tetlet.2010.04.105) the elegant diastereoselective Pd-catalyzed bis-methoxycarbonylation of 19 to the diester 20. Matthew S. Sigman of the University of Utah established (J. Am. Chem. Soc. 2010, 132, 13981. DOI: 10.1021/ja1060998) the oxidative Heck arylation of 21 to 23.

F. Dean Toste of the University of California, Berkeley found (Org. Lett. 2010, 12, 4728. DOI: 10.1021/ol102194c) that the intermediate in the gold-catalyzed alkoxylation of 24 could couple to an aryl silane 25 to give 26. Chun-Yu Ho of the Chinese University of Hong Kong used (Angew. Chem. Int. Ed. 2010, 49, 9182. DOI: 10.1002/anie.201001849) a Ni catalyst to add styrene 27 to the alkene 24. Masahiro Miura of Osaka University effected (J. Org. Chem. 2010, 75, 5421. DOI: 10.1021/jo101214y) the oxidative coupling of 29 with styrene 27 to give the linear product 30.

Several years ago (J. Am. Chem. Soc. 1996, 118, 4198. DOI: 10.1021/ja954147f), Jin Kun Cha, now at Wayne State University, reported a modified Kulinkovich protocol for coupling an ester with an alkene to give the cyclopropanol. Timothy W. Funk of Gettysburg College developed (Tetrahedron Lett. 2010, 51, 6726. DOI: 10.1016/j.tetlet.2010.10.067) an Ir catalyst for the specific cleavage of the cyclopropanol, effecting the net homologation of an alkene 31 to the branched ketone 32.

D. F. Taber, Org. Chem. Highlights 2011, September 19.