Synthesis, Table of Contents PAPER © Georg Thieme Verlag Stuttgart · New York An Efficient Stereoselective Synthesis of (E)-β-Fluoroalkenyliodonium Salts Masanori Yoshida*, Keiji Kawakami, Shoji Hara*Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, 060-8628, JapanFax: +81(11)7066557; e-Mail: myoshida@org-mc.eng.hokudai.ac.jp; Recommend Article Abstract Buy Article All articles of this category Abstract Stereoselective synthesis of (E)-β-fluoroalkenyliodonium salts was performed by the treatment of alk-1-ynes with p-iodotoluene difluoride in the presence of HBF4-Et2O. The reaction occurred instantaneously at -78 °C to give the fluoroalkenyliodonium salts in good yields with high stereoselectivity. The Pd-catalyzed carbomethoxylation of the fluoroalkenyliodonium salt was also carried out to obtain a (E)-β-fluoro-α,β-unsaturated ester. Key words iodonium salt - fluoroalkene - p-iodotoluene difluoride - stereoselective synthesis - fluorination reaction Full Text References References 1a Welch JT. Eswarakrishnan S. Fluorine in Bioorganic Chemistry Wiley; New York: 1991. 1b Welch JT. Tetrahedron 1987, 43: 3123 1c Ismail FMD. J. Fluorine Chem. 2002, 118: 27 1d Smart BE. J. Fluorine Chem. 2001, 109: 3 2a Kim BT. Min YK. Asami T. Park NK. Kwon OY. Cho KY. Yoshida S. Tetrahedron Lett. 1997, 38: 1797 2b Masnyl M. Fried J. Tetrahedron Lett. 1989, 30: 3243 2c Grieco PA. Takigawa T. Vedananda TR. J. Org. Chem. 1985, 50: 3111 2d Grieco PA. Schillinger WJ. Yokoyama Y. J. Med. Chem. 1980, 23: 1077 3a Okada M. Nakamura Y. Saito A. Sato A. Horikawa H. Taguchi T. Tetrahedron Lett. 2002, 43: 5845 3b Otaka A. Watanabe H. Yukimasa A. Oishi S. Tamamura H. Fujii N. Tetrahedron Lett. 2001, 42: 5443 3c Peng S. Qing F.-L. Li Y.-Q. Hu C.-M. J. Org. Chem. 2000, 65: 694 3d Huang X.-H. He P.-Y. Shi G.-Q. J. Org. Chem. 2000, 65: 627 3e Brown SJ. Corr S. Percy JM. Tetrahedron Lett. 2000, 41: 5269 3f Chevrie D. Lequeux T. Pommelet J.-C. Org. Lett. 1999, 1: 1539 3g Percy JM. Prime ME. J. Fluorine Chem. 1999, 100: 147 3h Lin J. Welch JT. Tetrahedron Lett. 1998, 39: 9613 3i Percy JM. Wilkes RD. Tetrahedron 1997, 53: 14749 3j Hossain MA. Tetrahedron Lett. 1997, 38: 49 3k Kuroboshi M. Yamada N. Takebe Y. Hiyama T. Tetrahedron Lett. 1995, 36: 6271 3l Clemenceau D. Cousseau J. Tetrahedron Lett. 1993, 34: 6903 3m Gillet JP. Sauvêtre R. Normant JF. Synthesis 1982, 297 4a Zhang X. Burton DJ. J. Fluorine Chem. 2001, 112: 317 4b Chen C. Wilcoxen K. Zhu Y.-F. Kim K.-I. McCarthy JR. J. Org. Chem. 1999, 64: 3476 4c Burton DJ. J. Fluorine Chem. 1999, 100: 177 4d Chen C. Wilcoxen K. Strack N. McCarthy JR. Tetrahedron Lett. 1999, 40: 827 4e Percy E. Singh M. Takahashi T. Takeuchi Y. Kirk KL. J. Fluorine Chem. 1998, 91: 5 4f McCarthy JR. Huber EW. Le T.-B. Laskovics FM. Matthews DP. Tetrahedron 1996, 52: 45 4g Patrick TB. Lanahan MV. Yang C. Walker JK. Hutchinson CL. Neal BE. J. Org. Chem. 1994, 59: 1210 4h Pirrung MC. Rowley EG. Holmes CP. J. Org. Chem. 1993, 58: 5683 4i McCarthy JR. Matthews DP. Stemerick DM. Huber EW. Bey P. Lippert BJ. Snyder RD. Sunkara PS. J. Am. Chem. Soc. 1991, 113: 7539 4j Burton DJ. J. Fluorine Chem. 1983, 23: 339 4k Moghadam GE. Penne JS. Bull. Soc. Chim. Fr. 1985, 448 5a Eddarir S. Francesch C. Mestdagh H. Rolando C. Bull. Soc. Chim. Fr. 1997, 134: 741 5b Eddarir S. Mestdagh H. Rolando C. Tetrahedron Lett. 1991, 32: 69 6a Carpenter W. J. Org. Chem. 1966, 31: 2688 6b Recent study: Sawaguchi M. Ayuba S. Hara S. Synthesis 2002, 1802 7 Hara S. Yoshida M. Fukuhara T. Yoneda N. Chem. Commun. 1998, 965 8a Hara S. Yamamoto K. Yoshida M. Fukuhara T. Yoneda N. Tetrahedron Lett. 1999, 40: 7815 8b Yoshida M. Hara S. Fukuhara T. Yoneda N. Tetrahedron Lett. 2000, 41: 3887 8c Yoshida M. Nagahara D. Fukuhara T. Yoneda N. Hara S. J. Chem. Soc., Perkin Trans. 1 2001, 2283 9 The stereochemistry was determined by 1H NMR. A vinylic hydrogen of 2a appeared at 6.70 ppm as a doublet (3 J H-F = 14.4 Hz), which was in good agreement with the reported data of a (E)-β-fluoroalkenyliodonium salt; see ref.7 A larger coupling constant (3 J H-F = 33.2 Hz) was observed from (Z)-2-fluorododecenyliodonium tetrafluoroborate: Yoshida M. Hara S. Org. Lett. 2003, 5: 573 10a Dehmlow EV. Lissel M. Liebigs Ann. Chem. 1980, 1: 1 10b Brandsma L. Preparative Acetylenic Chemistry Elsevier; Amsterdam: 1971. 10c Khan NA. Org. Synth. Coll. Vol. IV Wiley; New York: 1963. p.969 10d Brandsma L. Verkruijsse HD. Synthesis of Acetylenes, Allenes and Cumulenes Elsevier; Amsterdam: 1981.
