Regioselective Control in the Palladium-Catalyzed Isomerization of Methylenecyclopropylcarbinols Using Acetic Acid as a Reagent

Abstract

Tuning the regioselectivity of the Pd-catalyzed isomerization of methylenecyclopropylcarbinols in acetic acid is achieved by a subtle choice of the ligand and/or solvent. When dioxane is used as the solvent, penta-2,4-dien-1-ols are formed, whereas when AsPh₃ is used as the ligand and toluene is used as the solvent, pent-4-enals are formed. A plausible reaction mechanism is discussed on the basis of the control experiments.

Key words

regioselectivity - palladium-catalyzed isomerization - methylenecyclopropylcarbinols - acetic acid

References and Notes

• 1a Brandi A. Goti A. Chem. Rev.  1998,  98:  589 
• 1b Carbocyclic Three-Membered Ring Compounds, In Houben-Weyl   Vol. E17a-E17c:  de Meijere A. Thieme; Stuttgart: 1996. 
• 1c Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev.  2003,  103:  1213 
• 1d For a recent review: Nakamura I. Yamamoto Y. Adv. Synth. Catal.  2002,  344:  111 
• 2a Nötzel MW. Rauch K. Labahn T. de Meijere A. Org. Lett.  2002,  4:  839 
• 2b Takauchi D. Dsakada K. Chem. Commun.  2002,  646 
• 2c de Meijere A. Leonov A. Heiner T. Noltemeyer M. Bes MT. Eur. J. Org. Chem.  2003,  472 
• 2d Belov VN. Savchenko AI. Sokolov VV. Straub A. de Meijere A. Eur. J. Org. Chem.  2003,  551 
• 2e de Meijere A. Kuchuk ID. Sokolov VV. Labahn T. Rauch K. Es-Sayed M. Krämer T. Eur. J. Org. Chem.  2003,  985 
• 2f Siriwardana AI. Nakamura I. Yamamoto Y. Tetrahedron Lett.  2003,  44:  4547 
• 2g Shi M. Shao L.-X. Xu B. Org. Lett.  2003,  5:  579 
• 2h Shao L.-X. Shi M. Adv. Synth. Catal.  2003,  345:  963 
• 2i Siriwardana AI. Nakamura I. Yamamoto Y. Tetrahedron Lett.  2003,  44:  985 
• 3a Shi M. Wang B.-Y. Huang J.-W. J. Org. Chem.  2005,  70:  5606 
• 3b Nuske H. Bräse S. Kozhushkov SI. de Meijere A. Chem. Eur. J.  2002,  8:  2350 ; and references cited therein
• For the preparation of methylenecyclopropylcarbinols:
• 4a Okuma K. Tanaka Y. Yoshihira K. Ezaki A. Koda G. Ohta H. Hara K. Kashimura S. J. Org. Chem.  1993,  58:  5915 
• 4b Lautens M. Delanghe PHM. J. Org. Chem.  1993,  58:  5037 
• 4c Corre ML. Hercouet A. Bessieres B. J. Org. Chem.  1994,  59:  5483 
• 5a Drew J. Letellier M. Morand P. Szabo AG. J. Org. Chem.  1987,  52:  4047 
• 5b Misumi S. Nakagawa M. Bull. Chem. Soc. Jpn.  1963,  36:  399 
• 5c Oida S. Chem. Pharm. Bull.  2000,  694:  303 
• 5d Ishii Y. Gao C. Xu W.-X. Iwasaki M. Hidai M. J. Org. Chem.  1993,  58:  6818 
• 5e Reddy AM. Rao VJ. J. Org. Chem.  1992,  57:  6727 
• 6a Baum AA. Tetrahedron Lett.  1972,  13:  1817 
• 6b Bowman WA. Stephenson PT. Young AR. Tetrahedron  1995,  51:  11445 
• 6c Tokuda M. Fujita H. Miyamato T. Suginome H. Tetrahedron  1993,  49:  2413 
• 8a Trost BM. Rise F. J. Am. Chem. Soc.  1987,  109:  3161 
• 8b Trost BM. Schmidt T. J. Am. Chem. Soc.  1988,  110:  2301 
• 8c Al-Masum M. Yamamoto Y. J. Am. Chem. Soc.  1998,  120:  3809 
• 8d Kadota I. Shibuya A. Gyoung Y.-S. Yamamoto Y. J. Am. Chem. Soc.  1998,  120:  10262 ; and references cited therein
• 8e Itazaki M. Nishihara Y. Osakada K. J. Org. Chem.  2002,  67:  6889 
• 8f Patil NT. Kadota I. Shibuya A. Gyoung Y.-S. Yamamoto Y. Adv. Synth. Catal.  2004,  346:  800 
• 9a Jeffery T. Tetrahedron Lett.  1991,  32:  2121 
• 9b Jeffery T. Tetrahedron Lett.  1990,  31:  6641 
• 9c Jeffery T. Tetrahedron Lett.  1993,  34:  1133 

7

Solvent effects have been omitted due to the limited space of a communication, but are available from the authors upon request.