Synthesis of Allenes by Palladium-Catalyzed S_N2′ Reaction of Indium Organometallics with Propargylic Esters

Abstract

Allenes have been efficiently prepared by the reaction of propargylic esters (benzoates, acetates, carbonates) with triorganoindium compounds (R₃In) under palladium catalysis, via an S_N2′ rearrangement. The reaction proceeds smoothly at room temperature with a variety of aryl-, alkenyl-, and alkynylindium reagents. The yields obtained are high and the regioselectivity is complete both in the case of terminal and nonterminal propargylic esters.

allenes - indium organometallics - palladium catalysis - propargylic esters - regioselective reactions

References

1 Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004. 

2 Hoffmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 

For general references, see:

3a Tsuji J. Mandai T. In Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004.  p.585 

3b Alexakis A. Pure Appl. Chem.  1992,  64:  387 

3c Hoffmann-Röder A. Krause N. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.51 

4a Pasto DJ. Hennion GF. Shults RH. Waterhouse A. Chou S.-K. J. Org. Chem.  1976,  41:  3496 

4b Jeffery-Luong T. Linstrumelle G. Tetrahedron Lett.  1980,  21:  5019 

5 Negishi E. Liu F. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002.  p.551 

6 Pérez I. Pérez Sestelo J. Maestro MA. Mouriño A. Sarandeses LA. J. Org. Chem.  1998,  63:  10074 

7a Pérez I. Pérez Sestelo J. Sarandeses LA. Org. Lett.  1999,  1:  1267 

7b Pérez I. Pérez Sestelo J. Sarandeses LA. J. Am. Chem. Soc.  2001,  123:  4155 

7c Pena MA. Pérez I. Pérez Sestelo J. Sarandeses LA. Chem. Commun.  2002,  2246 

7d Pena MA. Pérez Sestelo J. Sarandeses LA. Synthesis  2003,  780 

7e Pena MA. Pérez Sestelo J. Sarandeses LA. Synthesis  2005,  485 

7f Pena MA. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2007,  72:  1271 

8a Rodríguez D. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2003,  68:  2518 

8b Baker L. Minehan T. J. Org. Chem.  2004,  69:  3957 

8c Rodríguez D. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2004,  69:  8136 

9 Riveiros R. Rodríguez D. Pérez Sestelo J. Sarandeses LA. Org. Lett.  2006,  8:  1403 

10a

DPEphos = bis[o-(diphenylphosphino)phenyl] ether.

10b Kranenburg M. van der Burgt YEM. Kamer PCJ. van Leeuwen PWNM. Goubitz K. Fraanje J. Organometallics  1995,  14:  3081 

10c Huang Z. Qian M. Babinski DJ. Negishi E. Organometallics  2005,  24:  475 

11a Rosini C. Giacomelli C. Salvadori P. J. Org. Chem.  1984,  49:  3394 

11b Wang S. Zhang L. J. Am. Chem. Soc.  2006,  128:  8414 

12

For general experimental methods, see ref. 8a.

13 Höffe G. Steglich W. Vorbrüggen H. Angew. Chem., Int. Ed. Engl.  1978,  17:  569 

14 Matsuda I. Komori K.-I. Itoh K. J. Am. Chem. Soc.  2002,  124:  9072 

15

Spectroscopic and analytical data for allenes 5-9 in Table [1] have been previously reported in ref. 9. Spectroscopic and analytical data for allenes 10-13 and 15-19 are reported herein.

16 Ruitenberg K. Kleijn H. Elsevier CJ. Meijer J. Vermeer P. Tetrahedron Lett.  1981,  22:  1451 

17 Caporusso AM. Zampieri A. Aronica LA. Banti D. J. Org. Chem.  2006,  71:  1902 

18 Jansen A. Krause N. Inorg. Chim. Acta  2006,  359:  1761