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Synlett 2009(6): 905-909  
DOI: 10.1055/s-0028-1088203
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Thieme Chemistry Journal Awardees - Where are They Now? Phosphine- and Water-Cocatalyzed [3+2] Cycloaddition Reactions of 2-Methyl-2,3-butadienoate with Fumarates: A Computational and Experimental Study

Yong Liang, Song Liu, Zhi-Xiang Yu*
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry, Peking University, Beijing 100871, P. R. of China
Fax: +86(10)62751708; e-Mail: yuzx@pku.edu.cn;
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Received 3 October 2008
Publikationsdatum:
16. März 2009 (online)

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Abstract

With the aid of computation and experiment, the phosphine- and water-cocatalyzed [3+2] cycloaddition reactions of 2-methyl-2,3-butadienoate with fumarates have been developed. In this reaction, 2-methyl-2,3-butadienoate is used as a three-carbon synthon generated through a water-catalyzed [1,4]-proton-shift process. The DFT calculations and isotopic labeling experiment have been done to explore how this [3+2] reaction occurs.

Key words

phosphine - water - organocatalysis - density functional calculations - reaction mechanisms

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5

In the revision of this paper, we repeated reaction (c) (Scheme  [²] ) twice. It was found that 3-CH2D-substituted [3+2] product was generated with a ratio of 44% and 38%, respectively. The 3-Me-substituted [3+2] product was formed through the catalysis of DOH (generated in the reaction) and H2O (generated and residual water in the reaction system). Therefore, it is reasonable for the observed deuterated ratio of about 40%.

12

Although the generation of zwitterion 13 is endergonic by 17.5 kcal mol-¹ in terms of free energy in benzene, the computed enthalpy and the free energy for the whole
[3+2] reaction in benzene is -39.6 and -25.8 kcal mol-¹, respectively.

14

General Procedure for the Ph 3 P- and H 2 O-Cocatalyzed [3+2] Reaction
To a mixture of the fumarate (1 mmol), Ph3P (0.5 mmol), and H2O (1 mmol) in toluene (5 mL) was added via syringe under nitrogen methyl 2-methylallenoate (0.5 mmol). After stirring at 90 ˚C for 12 h, the solvent was removed under reduced pressure, and the residue was purified by flash chromatography on SiO2 to yield the product.
trans -Trimethyl 3-Methylcyclopent-3-ene-1,2,4-tricarboxylate (3)
Colorless oil; R f  = 0.27 (PE-EtOAc, 6:1). ¹H NMR (300 MHz, CDCl3): δ = 2.13 (m, 3 H), 2.90 (ddm, J = 16.5, 6.6 Hz, 1 H), 3.08 (ddm, J = 16.5, 9.6 Hz, 1 H), 3.50 (dt, J = 9.6, 6.6 Hz, 1 H), 3.72 (s, 3 H), 3.74 (s, 3 H), 3.77 (s, 3 H), 3.96 (dm, J = 6.6 Hz, 1 H). ¹³C NMR (75.5 MHz, CDCl3): δ = 14.8, 36.0, 43.4, 51.3, 52.3, 52.4, 59.1, 128.2, 149.7, 165.3, 172.3, 174.0. IR: ν = 1717, 1735 cm -¹. MS (EI): m/z (%) = 256 (5) [M+], 224 (63), 196 (76), 164 (100). HRMS: m/z calcd for C12H16O6: 256.0947; found: 256.0950.
trans -1,2-Diethyl-4-methyl 3-Methylcyclopent-3-ene-1,2,4-tricarboxylate (5)
Colorless oil; R f  = 0.37 (PE-EtOAc, 6:1). ¹H NMR (300 MHz, CDCl3): δ = 1.27 (t, J = 7.2 Hz, 3 H), 1.30 (t, J = 7.2 Hz, 3 H), 2.14 (m, 3 H), 2.88 (ddm, J = 16.5, 6.6 Hz, 1 H), 3.08 (ddm, J = 16.5, 9.6 Hz, 1 H), 3.48 (dt, J = 9.6, 6.6 Hz, 1 H), 3.74 (s, 3 H), 3.93 (dm, J = 6.6 Hz, 1 H), 4.14-4.27 (m, 4 H). ¹³C NMR (75.5 MHz, CDCl3): δ = 14.09, 14.15, 14.8, 35.9, 43.5, 51.2, 59.3, 61.0, 61.3, 128.1, 149.9, 165.4, 171.8, 173.6. IR: ν = 1717, 1732 cm-¹. MS (EI): m/z (%) = 284 (6) [M+], 252 (13), 238 (53), 210 (100). HRMS: m/z calcd for C14H20O6: 284.1260; found: 284.1257.
trans -1,2-Diallyl-4-methyl 3-Methylcyclopent-3-ene-1,2,4-tricarboxylate (7)
Colorless oil; R f  = 0.36 (PE-EtOAc, 6:1). ¹H NMR (300 MHz, CDCl3): δ = 2.14 (m, 3 H), 2.91 (ddm, J = 16.5, 6.6 Hz, 1 H), 3.10 (ddm, J = 16.5, 9.6 Hz, 1 H), 3.54 (dt, J = 9.6, 6.6 Hz, 1 H), 3.74 (s, 3 H), 3.99 (dm, J = 6.6 Hz, 1 H), 4.60-4.67 (m, 4 H), 5.23-5.39 (m, 4 H), 5.85-6.00 (m, 2 H). ¹³C NMR (75.5 MHz, CDCl3): δ = 14.8, 35.9, 43.5, 51.3, 59.2, 65.6, 65.9, 118.4, 118.8, 128.2, 131.5, 131.7, 149.7, 165.3, 171.4, 173.2. IR: ν = 1717, 1733 cm-¹. MS (EI): m/z (%) = 308 (3) [M+], 276 (5), 250 (20), 222 (18), 41 (100). HRMS: m/z calcd for C16H20O6: 308.1260; found: 308.1252.