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DOI: 10.1055/s-0028-1088203
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
Publikationsverlauf
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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References and Notes
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%.
12Although 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.
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.