Synlett 2004(7): 1288-1290  
DOI: 10.1055/s-2004-822918
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Preparation of Deuteriated Dienes by Ring Fragmentation of Metallated Cyclopropylcarbinols

Elinor Zohar, Mirit Ram, Ilan Marek*
Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Technion City, 32000 Haifa, Israel
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Further Information

Publication History

Received 15 February 2004
Publication Date:
28 April 2004 (online)


The hydroalumination reaction of cyclopropenylcarbinols initially leads to the alumino-cyclopropylcarbinol derivatives, which is followed by an elimination reaction to give the corresponding substituted dienes as unique isomers and in good yields. The use of LiAlD4 as reducing agent provides stereoselectively substituted deuteriodienes.


  • 1a Mori K. The Synthesis of Insect Pheromones, In The Total Synthesis of Natural Products   Apsimon J. Wiley; New York: 1981. 
  • 1b Henrick CA. Tetrahedron  1977,  33:  1845 
  • 1c Rossi R. Synthesis  1977,  817 
  • 2a Nicolaou KC. Snyder SA. Montagnon T. Vassilikogiannakis G. Angew. Chem., Int. Ed.  2002,  41:  1668 
  • 2b Brockson TJ. Correa AG. Naves RM. Silva F. Catani V. Ceschi MA. Zukerman-Schpector J. Toloi AP. Ferreira ML. Brocksom U. Org. Synth.: Theory Appl.  2001,  5:  39 
  • 3 Kolodiazhnyi OI. In Phosphorous Ylides   Wiley-VCH; Weinheim: 1999. 
  • 4a Naso F. Pure Appl. Chem.  1988,  60:  79 
  • 4b Fiandese V. Marchese G. Naso F. Ronzini L. Synthesis  1987,  1034 ; and references cited therein
  • 5 Suzuki A. Cross-Coupling Reactions of Organoboron Compounds with Organic Halides, In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.49 
  • 6 Negishi E. Liu F. Palladium- or Nickel-Catalyzed Cross Coupling with Organometals Containing Zinc, Magnesium, Aluminium, and Zirconium, In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.1 
  • 7a Gardette M. Jabri N. Alexakis A. Normant JF. Tetrahedron  1984,  40:  2741 
  • 7b Normant JF. Alexakis A. Synthesis  1981,  841 
  • 8 Negishi E. Takahashi T. Baba S. Van Horn DE. Okukado N. J. Am. Chem. Soc.  1987,  109:  2393 
  • 9 Lipshutz BH. Pfeiffer SS. Noson K. Tomioka T. Hydrozirconation and Further Transmetalation Reactions, In Titanium and Zirconium in Organic Synthesis   Marek I. Wiley-VCH; Weinheim: 2002.  p.110 
  • 10a Furstner A. Leitner A. Mendez M. Krause H. J. Am. Chem. Soc.  2002,  124:  13856 
  • 11 Mitchell TN. Organotin Reagents in Cross-Coupling, In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.167 
  • 12 Kuck D. Mormann M. In Mass Spectrometry and Gas-Phase Ion Chemistry of Dienes and Polyenes, In The Chemistry of Dienes and Polyenes   Rappoport Z. Wiley; Chichester: 2000.  p.1 
  • 13 Duffault J.-M. Einhorn J. Alexakis A. Tetrahedron Lett.  1995,  36:  2765 
  • 14 Zohar E. Marek I. Org. Lett.  2004,  6:  341 
  • 15a Baird MS. Hussain HH. Nethercott W. J. Chem. Soc., Perkin Trans. 1  1986,  1845 
  • 15b Baird MS. Nethercott W. Tetrahedron Lett.  1983,  24:  605 
  • 15c Baird MS. Hussain HH. Tetrahedron  1987,  43:  215 
  • 15d Al-Dulayymi JR. Baird MS. Tetrahedron Lett.  1988,  29:  6147 
  • 15e Al-Dulayymi JR. Baird MS. Tetrahedron  1989,  45:  7601 
  • 15f Al-Dulayymi AR. Baird MS. J. Chem. Soc., Perkin Trans. 1  1994,  1547 
  • Rearrangements of cyclopropanols into dienes under acidic catalysis were reported:
  • 16a Il’ina NA. Kulinkovitch OG. Zh. Org. Khim.  1992,  28:  1597 
  • 16b Il’ina NA. Kulinkovitch OG. J. Org. Chem. USSR (Engl. Transl.)  1992,  28:  1272 
  • 16c Kulinkovitch OG. Tishchenko IG. Roslik NA. Reznikov IV. Synthesis  1983,  383 
  • 16d Patro B. Ila H. Junjappa H. Tetrahedron Lett.  1992,  33:  809 

General Procedure for the Preparation of Dienes from Cyclopropenylcarbinols 1a-g: LiAlH4 (or LiAlD4, 1 M solution in Et2O, 1 mmol) was added to a stirred solution of 1a-g (1 mmol) in 5 mL of benzene at 5 °C. The reaction mixture was then heated to 80 °C for several hours and the sequential reduction and elimination reactions were followed by TLC. When the transformation was complete, 1 M aq solution of HCl (3 mL) was added and the aqueous layer was extracted with Et2O (3 × 5 mL). The combined organic phases were dried over MgSO4, filtered and the solvent was removed under reduced pressure. Chromatography on silica gel (eluent: hexane) gave the dienes 4a-k in yields indicated in Table [1] .