Convenient and Efficient Access to Fluoroalkylated Vinylphosphonates via Highly Regio- and Stereoselective Hydrometalation or Carbometalation Reactions of Fluorine-Containing Alkynylphosphonates

Abstract

The hydrostannation, carbocupration, and carbozincation reactions of fluorinated alkynylphosphonates were investigated. The hydrostannation reaction proceeded smoothly without an additive (e.g., BEt₃/O₂, AIBN) to give the corresponding vinylstannanes in a highly regio- and stereoselective manner. Various cuprates, prepared from organolithium, Grignard, and organozinc reagents, could participate nicely in the carbocupration reactions, the corresponding adducts were obtained in good to high yields. Dialkylzinc reagents reacted smoothly with the alkynylphosphonates even in the absence of copper salt to afford the corresponding adducts in good yields.

Key words

fluoroalkenes - alkynylphosphonates - hydrostannation - carbocupration - carbozincation - regioselective - stereoselective

References

• 1a Quntar AAA. Srebnik M. J. Org. Chem.  2006,  71:  730 
• 1b Panarina AE. Dogadina AV. Ionin BI. Russ. J. Gen. Chem. (Engl. Transl.)  2003,  73:  1729 
• 1c Quntar AAA. Baum O. Shibli A. Dembitsky VM. Srebnik M. Angew. Chem. Int. Ed.  2003,  42:  4777 
• 1d Gil JM. Oh Y. J. Org. Chem.  1999,  64:  2950 
• 1e Quntar AAA. Melman A. Srebnik M. Synlett  2002,  61 
• 1f Quntar AAA. Srebnik M. J. Org. Chem.  2001,  66:  6650 
• 1g Quntar AAA. Melman A. Srebnik M. J. Org. Chem.  2002,  67:  3769 
• 1h Quntar AAA. Dembitsky VM. Srebnik M. Org. Lett.  2003,  5:  357 
• 1i Pergamont I. Srebnik M. Org. Lett.  2001,  3:  217 
• 1j Quntar AAA. Srebnik M. Chem. Commun.  2003,  58 
• 1k Ben-Valid S. Quntar AAA. Srebnik M. J. Org. Chem.  2005,  70:  3554 
• 1l Pergamont I. Srebnik M. Tetrahedron Lett.  2001,  42:  8059 
• 1m Quntar AAA. Srebnik M. Org. Lett.  2001,  3:  1379 
• 1n Quntar AAA. Rosenthal D. Srebnik M. Tetrahedron  2006,  62:  5995 
• 1o Baum O. Quntar AAA. Dembitsky VM. Srebnik M. Tetrahedron  2004,  60:  1359 
• 2a Harnden R. Parkin A. Parratt J. Perkin R. J. Med. Chem.  1993,  36:  1343 
• 2b Smeyers Y. Sanchez F. Laguna A. Ibanez N. Ruano E. Perez S. J. Pharm. Sci.  1987,  76:  753 
• 2c Megati S. Phadtare S. Zemlicka J. J. Org. Chem.  1992,  57:  2320 
• 2d Lazrek H. Rochdi A. Khaider H. Barascut J. Imbach J. Balzarini J. Witvrouw M. Pannecouque C. De Clerq E. Tetrahedron  1998,  54:  3807 
• 3a Minami T. Motoyashiya J. Synthesis  1992,  333 
• 3b Thomas AL. Sharpless KB. J. Org. Chem.  1999,  64:  8379 
• 3c Lee S. Lee B. Lee C. Oh D. Synth. Commun.  1999,  29:  3621 
• 3d Telan L. Poon C. Evans S. J. Org. Chem.  1996,  61:  7455 
• 3e Zhao Y. Pey C. Wong Z. Xi S. Phosphorus, Sulfur Silicon Relat. Elem.  1992,  66:  115 
• 3f Kim D. Rhie D. Tetrahedron  1997,  53:  13603 
• 3g Nagaoka Y. Tomioka K. J. Org. Chem.  1998,  63:  6428 
• 3h Defacqz N. Touillaux R. Marchand-Brynaert J. J. Chem. Res., Synop.  1998,  512 
• 4a Jin JI, and Hua JCH. inventors; US  3925506. 
• 4b Fujimatsu M, and Miura M. inventors; JP  63105108. 
• 4c Spak AJ, and Yu AJ. inventors; US  4088710. 
• 4d Fuller BS, Ellis WD, and Rowell RM. inventors; US  5683820. 
• 5a Shukla JR. inventors; US  4241145. 
• 5b Welch C. Gonzalez E. Guthrie J. J. Org. Chem.  1961,  26:  3270 
• 6 Ebdon JR. Recent Adv. Flame Retard. Polym. Mater.  1997,  8:  161 
• For reviews, see:
• 7a Mikami K. Itoh Y. Yamanaka M. Chem. Rev.  2004,  104:  1 
• 7b Qiu X.-L. Meng W.-D. Qing F.-L. Tetrahedron  2004,  60:  6711 
• 7c Dave R. Badet B. Meffre P. Amino Acids  2003,  24:  245 
• 7d Steenis JHV. Gen AVD. J. Chem. Soc., Perkin Trans. 1  2002,  2117 
• 7e Singh RP. Shreeve JM. Tetrahedron  2000,  56:  7613 
• 7f Prakash GKS. Yudin AK. Chem. Rev.  1997,  97:  757 
• 7g McClinton MA. McClinton DA. Tetrahedron  1992,  48:  6555 
• 8a Romanenko VD. Kukhar VP. Chem. Rev.  2006,  106:  3868 
• 8b Shen Y. Zheng J. Xin Y. Lin X. Qi M. J. Chem. Soc., Perkin Trans. 1  1995,  997 
• 8c Shen Y. Zhang Y. Jiang G.-F. Synthesis  2002,  714 
• 8d Shen Y. Zhang Y. Sun J. J. Fluorine Chem.  2002,  116:  157 
• 9 Shen Y. Qi M. J. Chem. Soc., Perkin Trans. 1  1993,  2153 
• 10 Chae J. Konno T. Kanda M. Ishihara T. Yamanaka T. J. Fluorine Chem.  2003,  120:  185 
• 11 Konno T. Takehana T. Chae J. Ishihara T. Yamanaka H. J. Org. Chem.  2004,  69:  2188 
• For the carbocupration reactions, see:
• 12a Konno T. Daitoh T. Noiri A. Chae J. Ishihara T. Yamanaka H. Org. Lett.  2004,  6:  933 
• 12b Konno T. Daitoh T. Noiri A. Chae J. Ishihara T. Yamanaka H. Tetrahedron  2005,  61:  9391 
• Organozinc reagents are well known as less reactive reagents, but some reports have already been published in which the organozinc reagents could react with some electrophiles smoothly even in the absence of copper salt, see:
• 13a Kim S. Lee JM. Tetrahedron Lett.  1990,  31:  7627 
• 13b Reddy CK. Devasagayaraj A. Knochel P. Tetrahedron Lett.  1996,  37:  4495 
• 13c Hanson MV. Rieke RD. J. Am. Chem. Soc.  1995,  117:  10775 
• 14a Drag M. Kafarski P. Pirat J.-L. Cristau H.-J. Phosphorus, Sulfur Silicon Relat. Elem.  2002,  177:  1153 
• 14b Cristau H.-J. Gasc M.-B. Mbianda XY. J. Organomet. Chem.  1994,  474:  C14 
• 14c Cristau H.-J. Mbianda XY. Beziat Y. Gasc M.-B. J. Organomet. Chem.  1997,  529:  301 
• 14d Huang X. Xiong Z.-C. Synth. Commun.  2003,  33:  2511