Highly Diastereoselective Electrophilic Fluorination of Cyclic syn-β-
Hydroxysilanes

Abstract

A synthesis of enantioenriched fluorinated carbocycles has been developed combining a sequential enantioselective silyl­allylboration-ring-closing metathesis with a highly diastereoselective electrophilic fluorination.

Key words

allylsilane - fluorine - stereoselectivity - silicon

References and Notes

• 1a Fleming I. Barbero A. Walter D. Chem. Rev.  1997,  2063 
• 1b Sarkar TK. In Science of Synthesis   Fleming I. Georg Thieme Verlag; Stuttgart: 2002.  p.837 
• 1c Denmark SE. Fu J. Chem. Rev.  2003,  2763 
• 1d Suga S. Nishida T. Yamada D. Nagaki A. Yoshida J. J. Am. Chem. Soc.  2004,  14338 
• 1e Fernandes RA. Yamamoto Y. J. Org. Chem.  2004,  735 
• 1f Evans DA. Aye Y. Wu J. Org. Lett.  2006,  2071 
• 1g Nair V. Dhanya R. Vidya N. Devipriya S. Synthesis  2006,  107 
• 1h Conchon E. Gelas-Mialhe Y. Remuson R. Tetrahedron: Asymmetry  2006,  1253 
• 1i Friestad GK. Korapala CS. Ding H. J. Org. Chem.  2006,  281 
• 2a

  For a recent review on the importance of fluorine in biological and medicinal chemistry, see a special issue of: ChemBioChem 2004, 5.

• 2b Bégué J.-P. Bonnet-Delpon D. J. Fluorine Chem.  2006,  992 
• 2c Kirk KL. J. Fluorine Chem.  2006,  1013 
• 2d Isanbor C. O’Hagan D. J. Fluorine Chem.  2006,  303 
• 2e Smart B. J. Fluorine Chem.  2001,  3 
• 3a Gouverneur V. Greedy B. Chem. Eur. J.  2002,  766 
• 3b Tredwell M. Gouverneur V. Org. Biomol. Chem.  2006,  26 
• 4a Greedy B. Paris J.-M. Vidal T. Gouverneur V. Angew. Chem. Int. Ed.  2003,  3291 
• 4b Thibaudeau S. Gouverneur V. Org. Lett.  2003,  4891 
• 4c Thibaudeau S. Fuller R. Gouverneur V. Org. Biomol. Chem.  2004,  1110 
• 4d Tredwell M. Tenza K. Pacheco MC. Gouverneur V. Org. Lett.  2005,  4495 
• 4e Giuffredi G. Bobbio C. Gouverneur V. J. Org. Chem.  2006,  5361 
• 5a Purser S. Odell B. Claridge TDW. Moore PR. Gouverneur V. Chem. Eur. J.  2006,  9176 
• 5b For the synthesis of 3, see: Carter MJ. Fleming I. Percival A. J. Chem. Soc., Perkin Trans. 1  1981,  2415 
• 6a Heo J.-N. Micalizio GC. Roush WR. Org. Lett.  2003,  1693 
• 6b Heo J.-N. Holson EB. Roush WR. Org. Lett.  2003,  1697 
• For sequential allyltitanation-ring-closing metathesis see:
• 6c de Fays L. Adam J.-M. Ghosez L. Tetrahedron Lett.  2003,  7197 
• 6d Adam J.-M. de Fays L. Laguerre M. Ghosez L. Tetrahedron  2004,  7325 
• 7 The synthesis of butenal is not trivial. For a multistep sequence, see: Crimmins MT. Kirincich SJ. Wells AJ. Choy AL. Synth. Commun.  1998,  3675 
• 8 Reuter JM. Sinha A. Salomon RG. J. Org. Chem.  1978,  43:  2438