Organic Chemistry Portal
Organic Chemistry Highlights

Monday, October 31, 2011
Douglass F. Taber
University of Delaware

Organic Functional Group Transformation

Susumu Saito of Nagoya University developed (Angew. Chem. Int. Ed. 2011, 50, 3006. DOI: 10.1002/anie.201006660) Fe-catalyzed conditions, compatible with alkenes, for converting an alcohol 1 to the amine 2. Corey R. J. Stephenson of Boston University took advantage (Nature Chem. 2011, 3, 140. DOI: 10.1038/nchem.949) of photoredox catalysis to convert an alcohol 3 to the iodide 4. Jing-Mei Huang of the South China University of Technology condensed (J. Org. Chem. 2011, 76, 3511. DOI: 10.1021/jo102455q) the halide 5 with benzaldehyde and aqueous ammonia to give the imine 6. Young Hoon Jung of Sungkyunkwan University used (Tetrahedron Lett. 2011, 52, 1901. DOI: 10.1016/j.tetlet.2011.02.036) chlorosulfonyl isocyanate to convert a benzylic (or allylic) ether 7 into the urethane 8.

David Crich of Centre de Recherche de Gif coupled (Org. Lett. 2011, 13, 2256. DOI: 10.1021/ol200531k) the isocyanate 9 with the acid 10 to give the amide 11. Tobias Ritter of Harvard University effected (J. Am. Chem. Soc. 2011, 133, 1760. DOI: 10.1021/ja108396k) α-hydroxylation of the acidic ketone 12 by exposure to O2 in the presence of a Pd catalyst. Gowravaram Sabitha of the Indian Institute of Chemical Technology, Hyderabad activated (Org. Lett. 2011, 13, 382. DOI: 10.1021/ol102658d) Pd(OH)2 by exposure to H2, then used the activated catalyst to isomerize the allylic alcohol 14 to the aldehyde 15. Richard C. Hartley of the University of Glasgow combined (Tetrahedron Lett. 2011, 52, 3020. DOI: 10.1016/j.tetlet.2011.04.017) commercial Nysted reagent and Cp2TiCl2 to methylenate the ester 16. The enol ether 17 is a versatile intermediate, giving, inter alia, the methyl ketone by hydrolysis, or the α-hydroxy ketone on exposure to peracid.

The activation of alkynes continues to be an area of vigorous investigation. Lukas Hintermann of the Technische Universität München devised (J. Am. Chem. Soc. 2011, 133, 8138. DOI: 10.1021/ja2026823) a Ru catalyst for the hydration of 18 to the aldehyde 19. Issa Yavari of Tarbiat Modares University effected (Tetrahedron Lett. 2011, 52, 668. DOI: 10.1016/j.tetlet.2010.11.135) oxidation of 20 to the N-sulfonyl amidine 22. Craig A. Merlic of UCLA coupled (Org. Lett. 2011, 13, 2778. DOI: 10.1021/ol2009297) 24 with the vinyl boronate derived from 23 to give the silyl enol ether 25. Li-Biao Han of AIST Tsukuba prepared (Chem. Commun. 2011, 47, 2333. DOI: 10.1039/C0CC03436C) 28 by adding 27 to 26.

The Meyer-Schuster rearrangement dates back almost 100 years. Tom D. Sheppard of University College London found (J. Org. Chem. 2011, 76, 1479. DOI: 10.1021/jo102263t) that simply adding CH3OH to the modern Au conditions assured clean conversion of 29 to 30. Cristina Nevado of the University of Zürich ran (Chem. Commun. 2011, 47, 248. DOI: 10.1039/C002679D) the rearrangement of 31 in the presence of Selectfluor, to give the α-fluoroenone 32.

D. F. Taber, Org. Chem. Highlights 2011, October 31.