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Monday, July 11, 2016
Douglass F. Taber
University of Delaware

Enantioselective Preparation of Alcohols and Amines: The Kunz Synthesis of Tetraponerine-8

Kuiling Ding of the Shanghai Institute of Organic Chemistry developed (Chem. Eur. J. 2015, 21, 16387. ) conditions for the enantioselective preparation of the β-aryloxy acid 2 by the hydrogenation of 1. Kazutaka Shibatomi of the Toyohashi University of Technology showed (Chem. Eur. J. 2015, 21, 14095. ) that 4 could be prepared by the enantioselective chlorination of 3 followed by displacement.

Xin-Yuan Liu and Bin Tan of the South China University of Science and Technology used (J. Am. Chem. Soc. 2015, 137, 14039. ) an enantioselective Passerini reaction to convert 5 to 7. Michael J. Krische of the University of Texas devised (J. Am. Chem. Soc. 2015, 137, 16024. ) a protocol for the preparation of 10 by the coupling of the alcohol 8 with 9. Peng Jiao of Beijing Normal University assembled (Org. Lett. 2015, 17, 3194. ) 13 by adding the nitronate 12 to the readily-prepared α-methylene aldehyde 11. James L. Leighton of Columbia University opened (Org. Lett. 2015, 17, 5858. ) the epoxide 14 with the alkyne 15 to give 16.

Xiang-Ping Hu of the Dalian Institute of Chemical Physics showed (ACS Catal. 2015, 5, 5026. ) that 18 could be prepared in high ee by the addition of phenylhydrazine to the racemic propargylic acetate 17. Stephen L. Buchwald of MIT achieved (Science 2015, 349, 62, ; J. Am. Chem. Soc. 2015, 137, 9716, ) high ee and high regioselectivity in the amination of 19, leading to 20.

Li Deng of Brandeis University assembled (Nature 2015, 523, 445. ) 23 in high ee by the conjugate addition to 22 of the anion derived from 21. Zheng Wang and Professor Ding achieved (J. Am. Chem. Soc. 2015, 137, 15346. ) high ee in the conversion of 24 to 25. Takanori Shibata of Waseda University effected (Chem. Commun. 2015, 51, 16660. ) enantioselective conjugate addition of 26 to 27 to give 28. The N-pyridyl group was readily removed. Till Opatz of the Johannes Gutenberg-University prepared (J. Org. Chem. 2015, 80, 6864. ) the α-quaternary amine 30 by the diastereoselective alkylation of 29.

Tetraponerine-8 (34), isolated from the toxin of the Papua New Guinean ant Tetraponera punctulata, is an efficient inhibitor of nicotinic acetylcholine receptors. En route to 34, Horst Kunz, also of Johannes Gutenberg-University, established (Synthesis 2015, 47, 2299. ) the second secondary amine of 33 by the D-arabinopyranosyl-directed hetero Diels-Alder addition of 31 to the Danishefsky diene 32.

D. F. Taber, Org. Chem. Highlights 2016, July 11.
URL: http://www.organic-chemistry.org/Highlights/2016/11July.shtm