Organic Chemistry Portal
Organic Chemistry Highlights

Monday, May 25, 2015
Douglass F. Taber
University of Delaware

Organic Functional Group Interconversion

Feng Li of the Nanjing University of Science and Technology devised (Chem. Commun. 2014, 50, 8303. DOI: 10.1039/C4CC02742F) a combination of reagents that directly converted the alcohol 1 to the protected amine 2. Yong-Sheng Bao and Bao Zhaorigetu of Inner Mongolia Normal University selectively (J. Org. Chem. 2014, 79, 6715. DOI: 10.1021/jo500877m) demethylated the tertiary amine 4, leading to the amide 5. Christopher W. Bielawski of the University of Texas developed (Chem. Eur. J. 2014, 20, 13487. DOI: 10.1002/chem.201403407) the reagent 7 for the conversion of an alcohol 6 to the bromide 8. The diiodo analogue of 7 also worked well.

Ross Denton of the University of Nottingham showed (Chem. Commun. 2014, 50, 7340. DOI: 10.1039/C4CC02171A) that the reagent 10 efficiently mediated the Mitsunobu coupling of 9 with benzoic acid to give 11. The other product of the reaction, Ph3P=O, could be converted back to 10. Silas P. Cook of Indiana University established (J. Am. Chem. Soc. 2014, 136, 9521. DOI: 10.1021/ja505199u) conditions for the selective conversion of the bromide 12 to the boronate 13. Gwilherm Evano of the Université Libre de Bruxelles converted (Chem. Commun. 2014, 50, 11907. DOI: 10.1039/C4CC05557H) the alkenyl iodide 14 to the nitrile 15 using acetone cyanohydrin as the nitrile anion source.

Seth B. Herzon of Yale University developed (Angew. Chem. Int. Ed. 2014, 53, 7892. DOI: 10.1002/anie.201404320) an improved Ru catalyst for the hydration of a terminal alkyne 16 to the aldehyde 17. Clément Mazet of the University of Geneva used (Chem. Commun. 2014, 50, 10592. DOI: 10.1039/C4CC05260A) an Ir catalyst for the isomerization of a 2,2-disubstituted epoxide 18 to the aldehyde 19. Laurent El Kaïm of the Ecole Polytechnique, Laurence Grimaud of UMPC, and Roland Jacquot and Philippe Marion of Solvay showed (Synthesis 2014, 46, 1802. DOI: 10.1055/s-0033-1341227) that in the presence of glutaronitrile 21, AlCl3 was an effective catalyst for the conversion of an acid 20 to the nitrile 22.

Yi-Si Feng and Hua-Jian Xu of the Hefei University of Technology found (Org. Lett. 2014, 16, 4586. DOI: 10.1021/ol502144c) that a carboxylic acid 23 could be coupled with diphenyl disulfide under decarboxylating conditions, leading to the sulfide 24. Kenneth M. Doll of USDA Peoria observed (ACS Catal. 2014, 4, 3517. DOI: 10.1021/cs501019t) that decarboxylation of the unsaturated carboxylic acid 25 with a Ru catalyst delivered the alkene 26 as a mixture of regioisomers. Orson L. Sydora of Chevron Phillips and Mark Stradiotto and Laura Turculet of Dalhousie University used (Chem. Eur. J. 2014, 20, 13918. DOI: 10.1002/chem.201403945) a Co catalyst to effect the room temperature equilibrating hydroboration of an internal alkene 27 to the terminal boronate 28.

Maddi Sridar Reddy of the Central Drug Research Institute rearranged (J. Org. Chem. 2014, 79, 823. DOI: 10.1021/jo402570t) the propargylic acetate 29 to the unsaturated amide 30. In a modern-day version of the Willgerodt reaction, Thanh Binh Nguyen of Gif-sur-Yvette prepared (Org. Lett. 2014, 16, 310. DOI: 10.1021/ol403345e) the thioamide 33 by coupling the alkyne 31 with the amine 32 in the presence of elemental sulfur.

D. F. Taber, Org. Chem. Highlights 2015, May 25.