Aqueous trimethylamine mediated Baylis-Hillman coupling of alkyl acrylates with aldehydes is described

Basavaiah, Deevi

Krishnamacharyulua, Marimganti

Raoa, Anumolu Jaganmohan

English

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The Aqueous Trimethylamine Mediated Baylis-Hillman Reaction
Deevi Basavaiaha; Marimganti Krishnamacharyulua; Anumolu Jaganmohan Raoa
a School of Chemistry, University of Hyderabad, Hyderabad, India
To cite this Article Basavaiah, Deevi , Krishnamacharyulu, Marimganti and Rao, Anumolu Jaganmohan(2000) 'The
Aqueous Trimethylamine Mediated Baylis-Hillman Reaction', Synthetic Communications, 30: 11, 2061 — 2069
To link to this Article: DOI: 10.1080/00397910008087256
URL: http://dx.doi.org/10.1080/00397910008087256
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SYNTHETIC COMMUNICATIONS, 30(1 l), 2061-2069 (2000) 
THE AQUEOUS TRIMETHYLAMINE MEDIATED 
BAYLIS-HILLMAN REACTION 
Deevi Basavaiah,' Marimganti Krishnamacharyulu and Anumolu 
Jaganmohan Rao 
School of Chemistry, University of Hyderabad, Hyderabad-500 046, India 
Abstract: Aqueous trimethylamine mediated Baylis-Hillman coupling of alkyl acrylates 
with aldehydes is described. 
The bicyclic tertiary amine (particularly DABCO) catalyzed Baylis- 
Hillman construction of carbon-carbon bond between the a-position of activated 
akenes and aldehydes producing a usefbl class of multifbnctional molecules (eq. 
1) and applications of these molecules in a variety of stereoselective transformat- 
ions have been well documented in the literature.' In continuation of our interest 
in Baylis-Hillman reaction: we herein report the application of aqueous 
trimethylamine in performing the Baylis-Hillman coupling between various alkyl 
acrylates and aldehydes. 
* To whom correspondence should be addressed 
206 1 
Copyright Q 2000 by Marcel Dekker, Inc. www.dekker.com 
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2062 BASAVAIAH, KRISI-INAMACHARYULU, AND JAGANMOHAN RAO 
OH 
EWG = COOMe, CN, COMe etc. 
R = alkyl, aryl 
Though DABCO has been the most commonly used catalyst for the 
Baylis-Hillman reaction, organic chemists have been interested in the 
development of other catalystdcatalytic systems such as DMAP,3 dimethyl 
~ulfide/TiC&,~ pyrrolizidines,’ phosphines6 etc. Carehl literature survey reveals 
that Nakagawa et ul. reported in 1995 in their European patent an aqueous 
trimethylamine mediated Baylis-Hillman reaction of paraformaldehyde with alkyl 
acrylates.’ With an objective to understand the scope of various amine catalysts 
in performing the Baylis-Hillman reaction, we have undertaken a systematic 
study on the efficacy of trimethylamine, the tertiary amine containing minimum 
number of carbon atoms, for performing the Baylis-Hillman reaction. In this 
direction first we examined the Baylis-Hillman reaction of 2-pyridinecarbo- 
xaldehyde with methyl acrylate in the presence of aqueous trimethylamine. The 
best results were obtained when a mixture of 2-pyridinecarboxaldehyde (10 
mmol), methyl acrylate (30 mmol) and aqueous trimethyl amine (30% w/v) (12 
mmol) was heated at 60°C for 4 hours thus providing the required methyl 3- 
hydroxy-2-methylene-3-(pyrid-2-yl)propanoate (1) in 62% yield after usual work 
up.8*9 Encouraged by the fastness of this reaction we then successhlly carried out 
the aq.Me3N catalyzed Baylis-Hillman coupling of representative alkyl acrylates 
with various reactive aldehydes (Scheme 1, Tables l 8 ~ 2 ) . ~  However similar 
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BAYLIS-HILLMAN REACTION 2063 
reaction of benzaldehyde and 4-chlorobenzaldehyde with methyl acrylate is 
extremely sluggish under these conditions. 
Scheme 1 
COOR * ArCHO (iCmR HCHO ~ 
aq. NMe 3 aq.NMe3 
SOOC, 6h 10-1 3 WOC. 4 - 5h 1 -9 
Ar = pyrid-2-yl, 4-nitrophenyl, fur-2-yl 
R = Me, Et, n-Bu 
R = Me, Et, n-Bu, I-Bu 
We also successfblly carried out the aqueous trimethylamine induced 
Baylis-Hillman reaction of paraformaldehyde with various alkyl acrylates thus 
providing a simple synthesis of alkyl 2-(hydroxymethyl)prop-2-enoates (10-13) 
in good yields (Scheme 1, Tables I &2).9 Alkyl 2-(hydroxymethyl)prop-2-enoates 
are important precursors for the synthesis of a-bromomethylacrylates and a- 
methylene-y-butyrolactones. '' 
Attempted Baylis-Hillman reaction of cyclohex-Zen- 1 -one with parafor- 
maldehyde in presence of aq. Me3N was not clean. However, cyclohex-2-en-l- 
one undergoes Michael type self dimerization in the presence of aqueous 
trimethylamine (30% w/v) (1.2 equivalents) to provide 2-(3-oxocyclohex- 1 -yl)cy- 
clohex-2-enone (14) in 35% yield (eq. 2, Table 2).",'* 
In conclusion, we have demonstrated the application of aqueous 
trimethylamine (which is readily available and cheap) as an alternative catalyst 
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2064 BASAVAIAH, KRISHNAMACHARYULU, AND JAGANMOHAN RAO 
COOEt 
COOBu" 
paraformaldehyde 
Table 1 : Aqueous trimethylamine mediated Baylis-Hillman reaction 
6 1112 66 
6 12 62 
2-pyridinecarboxaldehyde 
4-nitrobemaldehyde 
I I I 1 COOBu' I 6 1 13" I 64 1 
a) all reactions of aromatic aldehydes were canied out on a 10 mmol scale of the aldehyde with 30 
mmol of akyl acrylate aad 12 mmol of aqueous himethylamine (30% wk) at 60-C. b) all 
d o n s  in the case of HCHO were canied out on a LOO mmol scale of HCHO with 200 mmol of 
alkyl acrylate and 120 mmol of aqueous trimethylamine (30% wh) at 6O'C. c) all products 
(except 4) were obtained as either colorless (1. 2, 10-13) or pale yellow oils (3, 5-9, 14); 
compound 4 was obtained as pale yellow crystals. d) yields of the isolated pure products after 
silica gel column chromatography (5% ethyl acetate in hexanes) (13) or distillation under 
reduced pressure (10-13) based on the aldehydes. 
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BAYLIS-HILLMAN REACTION 2067 
for the Baylis-Hillman reaction of reactive aldehydes and formaldehyde with 
various alkyl acrylates. 
Acknowledgements: We thank DST (New Delhi) for funding this project. We thank 
UGC (New D e b )  for the Special Assistance Program in Organic Chemistry in the 
School of Chemistry, University of Hyderabad. MK thanks UGC (New Delhi) and AJR 
thanks CSIR (New Delhi) for financial support. 
REFERENCES AND NOTES: 
I .  
2. 
3. 
4. 
5 .  
6. 
7. 
8. 
9. 
a) Basavaiah, D.; Dharma Rao, P.; Suguna Hyma, R. Tetrahedron, 1996, 52, 800 1. 
b) Ciganek, E. Organic Reactions. 1997, vol.51. pp 201-350 (Paquette, L.A., 
Editor), John Wiley & Sons, New York. c) Drewes, S.E.; Roos, G.H.P. 
Tetrahedron, 1988, 44,4653. 
a) Basavaiah, D.; Bakthadoss, M.; Pandiaraju, S. Chem. Commun.. 1998, 1639. b) 
Basavaiah, D.; Krishnamacharyulu, M.; Suguna Hyma, R.; Pandiaraju. S .  
Tetrahedron Lett., 1997. 38, 2141. c) Basavaiah, D.; Krishnamacharyulu, M.; 
Suguna Hyma, R.; Sarma, P.K.S.; Kumaragurubaran, N. J.  Org.Chem., 1999, 64, 
1197. d) Basavaiah, D.: Sarma, P.K.S.; Bhavani, A.K.D. J.  Chem. Soc., Chem. 
Commun., 1994, 1091. 
Rezgui, F.; El Gaied, M.M. TetrahedronLett., 1998,39,5965. 
Kataoka, T.; Iwama, T.; Tsujiyama, S .  Chem. Commun.. 1998, 197. 
Barrett, A.G.M.; Cook, AS.; Kamimura, A. Chhem. Commun., 1998,2533. 
Hayase, T.; Shibata, T.; Soai, K.; Wakatsuki, Y. Chem. Commun.. 1998, 1271. 
Nakagawa, K.; Makino, M.; Kita, Y. Eur. Patent Appl. Ep 669.312 (1995): Chem. 
Abstr., 1995, 123, 285218~. 
This molecule is known in the literature and was prepared via the DABCO 
catalyzed coupling of 2-pyridinecarboxaldehyde with methyl acrylate in CHC13 for 
3 days in 94% yield. See: Bode, M.L.; Kaye, P.T. J.  Chem. Soc., Perkm Trans. 1 .  
1993,1809. 
Preparation of molecule 1 (Representative procedure): A mixture of pyridine-2- 
carboxaldehyde (10 mmol, 1.071 g), methyl acrylate (30 mmol, 2.583 g) and 
aqueous trimethylamine (30% w/v) (12 mmol, 2.36 mL) was heated at 6OoC for 4 
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2068 BASAVAIAH, KRISHNAMACHARWLU, AND JAGANMOHAN RAO 
10. 
11. 
12. 
I?  
## 
hours. The reaction mixture was then cooled to room temperature, layers separated 
and the aqueous layer was extracted with ether (3 x10 mL). The combined organic 
layer was dried over anhydrous sodium sulfate, concentrated and silica gel column 
chromatography (5% ethyl acetate in hexanes) of the crude product thus obtained, 
has provided 1.196 g (62%) of methyl 3-hydroxy-2-methylene-3-@yrid-2- 
y1)propanoate (1) as a colorless oil. 
a) Masuyama, Y.; Nimura, Y.; Kurusu, Y. Tetrahedron Letf., 1991, 32, 225. b) 
Drewes, S.E.; Loizou, G.; Roos, G.H.P. Synth. Commun., 1987,17,291. 
Preparation of molecule 14: A mixture of cyclohex-2en-l-one (20 mmol, 1.923 
g) and aqueous trimethylmine (30% w/v) (24 mmol, 4.72 mL) was heated at 60°C 
for 6 hours. Usual work up followed by silica gel column chromatography (10% 
ethyl acetate in hexanes) has provided 0.680 g (35%) of 14 as pale yellow oil. 
These molecules are known, and their spectral data (IR, IH and/or I3C NMR) are 
reported in the literature. Spectral data of these molecules are agreement with the 
literature data. For molecule 1, see: Foucaud, A,; El Guemmout, F. Bull. SOC. 
Chim. Fr., 1989, 403. For molecule 2, see: ref 8. For molecule 4, see: ref 15. For 
molecules 7 and 9, see: Fort, Y,; Berthe, M.C.; Caubere, P. Tetruhedron, 1992, 48. 
6371. For molecule 10, see: ref lob. For molecule 11, see: ref 16. For molecule 
13, see: Novarro, C.; Castaing, M.D-; Colombani, D.; Maillard, B. Synth. 
Commun., 1993, 23, 1025. For molecule 14, see: Mubarak, M.S.; Pagel, M.; 
Marcus, L.M.; Peters, D.G. 1 Org. Chem., 1998.63.1319. 
Elemental analysis of selected products:'.@ 
Product 
1 
2 
3 
5 
6 
8 
12 
14 .- .. - 
:mental analysis is furnished 1 
C 
62.01 (62.17) 
63.98 (63.76) 
66.62 (66.36) 
57.19 (57.37) 
60.45 (60.21) 
61.51 (61.22) 
60.84 (60.74) 
74.66 (74.97) 
either unknow 
Found (Calcd.) (%) 
H 
5.77 (5.74) 
6.36 (6.32) 
7.27 (7.28) 
5.24 (5.22) 
6.10 (6.14) 
6.13 (6.16) 
8.95 (8.92) 
8.34 (8.39) 
N 
7.28 (7.25) 
6.73 (6.76) 
5.99 (5.95) 
5.56 (5.58) 
5.03 (5.02) ___ 
_I 
- 
iown molecules 
whose spectral data is not fully reported in the literature. 
@ Recorded on a Perkin-Elmer 24OC-CHN analyzer. 
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BAYLIS-HILLMAN REACTION 2069 
14. Compound 4: m.p.: 72-73°C (lit." 74°C); Compound 10: b.p.: 71-72OC/2mm; 
Compound 11: b.p.: 78-8OoC/2mm (lit.I6 65-7OoC/lmm); Compound 12: b.p.: 
80°C/0.5mm; Compound 13: b.p.: 76"C/OSmm. 
Foucaud, A.; Rouille, E. Synthesis, 1990. 787. 
Villieras, J.; Rambaud, M. Synthesis, 1982, 11, 924. 
15. 
16. 
Accepted 9/11/99 
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The aqueous trimethylamine mediated Baylis-Hillman reaction

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The aqueous trimethylamine mediated Baylis-Hillman reaction

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