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.

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 

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.

12 MacCallum JL. Tieleman DP. J. Am. Chem. Soc.  2002,  124:  15085