Tandem-Directed Regioselective Hydroformylation/β-Elimination: A Practical Method for the Synthesis of Enals

Abstract

A practical synthesis of α,β-unsaturated aldehydes by a tandem-directed hydroformylation/β-elimination process of allylic o-DPPB esters is reported. The o-DPPB group served as an effective controller for regioselectivity of the hydroformylation towards the desired aldolate isomer, and was subsequently eliminated in situ by mild standard bases. The reaction is rather general for the preparation of 1,1-disubstituted and trisubstituted enals and is compatible with many functional groups. Recovery of the o-DPPBA is possible either by chromatography or precipitation as the diethyl­ammonium salt.

Key words

hydroformylation - enals - tandem reaction - aldehydes - rhodium

References

• 1 Wichard T. Göbel C. Feussner I. Pohnert G. Angew. Chem. Int. Ed.  2005,  44:  158 ; Angew. Chem. 2005, 116, 161
• 2 Rowe DJ. Perf. Flav.  2000,  25:  1 
• 3 Mackie PR. Foster CE. In Comprehensive Organic Functional Group Transformations II   Vol. 3:  Katritzky AR. Taylor RJK. Pergamon; Oxford: 2005.  p.59-97  
• 4 Escher I. Glorius F. In Science of Synthesis   Vol. 25:  Brückner R. Thieme; Stuttgart: 2007.  p.733-777  
• 5a Olah GA. Arvanaghi M. Angew. Chem., Int. Ed. Engl.  1981,  20:  878 ; Angew. Chem. 1981, 93, 925
• 5b

  For more examples see ref. 4.

• 6 Crimmins MT. King BW. J. Am. Chem. Soc.  1998,  120:  9084 
• 7a Wittig G. Reiff H. Angew. Chem., Int. Ed. Engl.  1968,  7:  7 ; Angew. Chem. 1968, 80, 8
• 7b Corey EJ. Enders D. Bock MG. Tetrahedron Lett.  1976,  17:  7 
• 8 Duhamel L. Gralak J. Bouyanzer A. Tetrahedron Lett.  1993,  34:  7745 
• 9 Wollenberg RH. Albizati KF. Peries R. J. Am. Chem. Soc.  1977,  99:  7365 
• 10 Trippet S. Walker DM. J. Chem. Soc.  1961,  1266 
• Applications:
• 11a Zhou G. Hu Q.-Y. Corey EJ. Org. Lett.  2003,  5:  3979 
• 11b Nagamitsu T. Takano D. Fukuda T. Otoguro K. Kuwajima I. Harigaya Y. Omura S. Org. Lett.  2004,  6:  1865 
• 12 Cresp TM. Sargent MV. Vogel P. J. Chem. Soc., Perkin Trans. 1  1974,  37 
• 13a Nagata W. Hayase Y. J. Chem. Soc. C  1969,  460 
• 13b Nagata W. Hayase Y. Tetrahedron Lett.  1968,  4359 
• 14 Johnson JR. Cuny GD. Buchwald SL. Angew. Chem., Int. Ed. Engl.  1995,  16:  1760 
• 15a Breit B. In Topics in Organometallic Chemistry, ‘Directed Metallation’   Vol. 24:  Chatani N. Springer; Berlin: 2007.  p.145-168  ; and references cited therein
• 15b Breit B. Acc. Chem. Res.  2003,  36:  264 ; and references cited therein
• 16 Breit B. Grünanger CU. Abillard O. Eur. J. Org. Chem.  2007,  2497 
• 17 Breit B. Acc. Chem. Res.  2003,  36:  264 
• 19 Grummit O. Splitter J. J. Am. Chem. Soc.  1952,  74:  3924 
• 20 Bergmeier SC. Stanchina DM. J. Org. Chem.  1997,  62:  4449 
• 21 Denmark SE. Harmata MA. White KS. J. Org. Chem.  1987,  52:  4031 
• 22 Ramiandrasod F. Descoins C. Synth. Commun.  1990,  20:  1989 
• 23 Zibuck R. Streiber JM. J. Org. Chem.  1989,  54:  4717 
• 24 Dodd DS. Oehlschlager AC. Georgopapadakou NH. Polak AM. Hartman PG. J. Org. Chem.  1992,  57:  7226 
• 25 Itoh T. Matsushita Y. Abe Y. Han S.-H. Wada S. Hayase S. Kawatsura M. Takai S. Morimoto M. Hirose Y. Chem. Eur. J.  2006,  12:  9228 
• 26 Mordini A. Peruzzi D. Russo F. Valacchi M. Reginato G. Brandi A. Tetrahedron  2005,  61:  3349 
• 27 Heng KK. Smith RAJ. Tetrahedron  1979,  35:  425 
• 28 Embrey MW. Fisher TE. Wai JS. Synth. Commun.  1996,  26:  3431 
• 29 Kobayashi Y. Yoshida S. Nakayama Y. Eur. J. Org. Chem.  2001,  1873 
• 30 Le Bideau F. Gilloir Y. Nilsson C. Aubert M. Malacria M. Tetrahedron  1996,  52:  7487 
• 31 Hong JH. Oh C.-H. Cho J.-H. Tetrahedron  2003,  59:  6103 
• 32 Hoots JE. Rauchfuss TB. Wrobleski D.-A. Inorg. Synth.  1982,  21:  175 
• 33 Varelis P. Johnson BL. Aust. J. Chem.  1997,  50:  43 
• 34 Ullrich F.-W. Rotscheidt K. Breitmaier E. Chem. Ber.  1986,  119:  1737 
• 35 Hu Q.-Z. Zhou G. Corey EJ. J. Am. Chem. Soc.  2004,  126:  13708 
• 36 Browder CC. Marmsäter FP. West FG. Org. Lett.  2001,  3:  3033 
• 37 Mizutani H. Watanabe M. Honda T. Tetrahedron  2002,  58:  8929 

18

For an E2 process, the formation of the Z-configured enals from the anti-aldolate hydroformylation products is expected.