Octanol-Accelerated Baylis-Hillman Reaction

Abstract

The Baylis-Hillman reaction was greatly accelerated by use of octanol as an additive. Under the octanol-accelerated Baylis-Hillman conditions, unactivated aldehydes such as aliphatic aldehydes and aromatic aldehydes with electron-withdrawing substituents were readily converted into the desired products in good to high yields.

Key words

Baylis-Hillman reaction - octanol - additive - rate acceleration - aliphatic aldehydes

References and Notes

• 1a Basavaiah D. Rao PD. Hyma RS. Tetrahedron  1996,  52:  8001 
• 1b Ciganek E. Org. React.  1997,  51:  201 
• 1c Langer P. Angew. Chem. Int. Ed.  2000,  39:  3049 
• 1d Basavaiah D. Rao AJ. Satyanayana T. Chem. Rev.  2003,  103:  811 
• 2a Kataoka T. Kinoshita H. Kinoshita S. Iwamura T. Watanabe S. Angew. Chem. Int. Ed.  2000,  39:  2358 
• 2b Shi M. Jiang J.-K. Feng YS. Org. Lett.  2000,  2:  2397 
• 2c Shi M. Jiang JK. Tetrahedron  2000,  56:  4793 
• 2d Li G. Wei HX. Gao JJ. Caputo TD. Tetrahedron Lett.  2000,  41:  1 
• 2e Shi M. Feng YS. J. Org. Chem.  2001,  66:  406 
• 2f Shi M. Jiang J.-K. Cui S.-C. Tetrahedron  2001,  57:  7343 
• 2g Patra A. Batra S. Joshi BS. Roy R. Kundu B. Bhaduri AP. J. Org. Chem.  2002,  67:  5783 
• 2h Basavaiah D. Sreenivasulu B. Rao AJ. J. Org. Chem.  2003,  68:  5983 
• 2i Pei W. Wei H. Li G. Chem. Commun.  2002,  1856 
• 2j Pei W. Wei H. Li G. Chem. Commun.  2002,  2412 
• 2k Kinoshita H. Kinoshita S. Munechika Y. Iwamura T. Watanabe S. Kataoka T. Eur. J. Org. Chem.  2003,  4852 
• 2l Kinoshita H. Osamura T. Kinoshita S. Iwamura T. Watanabe S. Kataoka T. Tanabe G. Muraoka O. J. Org. Chem.  2003,  68:  7532 
• 3 Kundu MK. Mukherjee SB. Balu N. Padmakumar R. Bhat SV. Synlett  1994,  444 
• 4a Drewes SE. Roos GHP. Tetrahedron  1988,  44:  4653 
• 4b Basavaiah D. Dharma Rao P. Suguna Hyma R. Tetrahedron  1996,  52:  8001 
• 4c Ciganek E. In Organic Reactions   Vol. 51:  Paquette LA. Wiley; New York: 1997.  p.201 
• 5a Ameer F. Drewes SE. Freese S. Kaye PT. Synth. Commun.  1988,  18:  495 
• 5b Drewes SE. Freese S. Emslie ND. Roos GHP. Synth. Commun.  1988,  18:  1565 
• 5c Basavaiah D. Sarma PKS. Synth. Commun.  1990,  20:  1611 
• 5d Bailey M. Marko IE. Ollis WD. Rasmussen PR. Tetrahedron Lett.  1990,  31:  4509 
• 6 Auge J. Lubin N. Lubineau A. Tetrahedron Lett.  1994,  35:  7947 
• 7a Almeida WP. Coelho F. Tetrahedron Lett.  1998,  39:  8609 
• 7b Coelho F. Almeida WP. Veronese D. Mateus CR. Silva Lopes EC. Rossi RC. Silveira GPC. Pavam CH. Tetrahedron  2002,  58:  7437 
• 8a Hill JS. Isaacs NS. Tetrahedron Lett.  1986,  27:  5007 
• 8b Hill JS. Isaacs NS. J. Chem. Res., Synop.  1988,  330 
• 8c Schuurman RJW. v. d. Linden A. Grimbergen RPF. Nolte RJM. Scheeren HW. Tetrahedron  1996,  52:  8307 
• 9 Shi M. Liu Y.-H. Org. Biomol. Chem.  2006,  4:  1468 
• 10 Aggarwal VK. Fulford SY. Lloyd-Jones GC. Angew. Chem. Int. Ed.  2005,  44:  1706 
• 12 MacCallum JL. Tieleman DP. J. Am. Chem. Soc.  2002,  124:  15085 

11

Spectroscopic Data for Compound 4.
IR (neat): 3415, 1665, 1635, 1088 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.32 (d, J = 6.5 Hz, 3 H), 2.36 (s, 3 H), 3.31 (br s, 1 H), 4.66 (br s, 1 H), 6.08 (s, 1 H), 6.11 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 200.19, 151.09, 124.27, 65.89, 25.90, 21.76. HRMS (ESI): m/z calcd for C₆H₁₀O₂ [M + H]: 114.0681; found: 114.0685.
Spectroscopic Data for Compound 6.
¹H NMR (400 MHz, CDCl₃): δ = 6.04 (s, 1 H), 5.85 (s, 1 H), 2.61-2.57 (m, 1 H), 2.55-2.50 (m, 1 H), 2.34 (s, 3 H), 2.13 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 207.59, 199.24, 147.52, 126.01, 42.20, 29.47, 25.61, 25.05.