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DOI: 10.1055/s-0030-1258056
A Practical and Highly Efficient Hydroacylation Reaction of Azodicarboxylates with Aldehydes in Water
Publication History
Publication Date:
19 August 2010 (online)

Abstract
The very efficient hydroacylation reaction of azodicarboxylates, with various aldehydes, was carried successfully out at room temperature in water without the use of a catalyst to obtain a variety of hydrazine imide products in high yields. A wide range of aldehydes, including aliphatic and aromatic compounds, was considered, and the reaction is believed to proceed via a radical mechanism, in which water plays an integral role in stabilizing the radical intermediate.
Key words
azo compounds - green chemistry - hydroacylation - aldehydes
- 1 These authors contributed equally
to this work
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References and notes
The reaction of hexanal and diisopropyl azodicarboxylate without catalyst under neat conditions was described by Lee et al.¹0a and afforded the addition product with 14 days at r.t.
13Due to the many byproducts observed in the reaction mixture, the bisazodicarboxylates could not be isolated.¹0a
15
Typical Procedure
for the Hydroacylation Reaction in H
2
O
To a stirred solution of aldehyde 1 (1.0 mmol) in H2O (0.5 mL)
was added azodicarboxylate 2 (0.5 mmol).
The reaction was stirred at r.t. for the time as indicated in Tables
[¹]
and
[²]
. The reaction mixture
was extracted with Et2O for two times (4 × 5
mL). The Et2O solution was combined, concentrated, and
purified by flash chromatography on silica gel (hexane-EtOAc = 4:1)
to afford the product 3.
Data
for the new hydroacylation products: Compound 3b: ¹H
NMR (400 MHz, CDCl3): δ = 6.57 (br,
1 H), 5.10-4.90 (m, 2 H), 2.94-2.84 (m, 2 H),
1.72-1.58 (m, 4 H), 1.40-1.15 (m, 20 H), 0.88
(t, J = 6.8
Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 173.9,
155.1, 152.6, 72.1, 70.4, 37.0, 31.8, 29.3, 29.2, 29.1, 24.7, 24.6,
22.6, 21.9, 21.7, 14.1 ppm. Anal. Calcd for C16H32N2O5Na [M + Na]+:
367.2209; found: 367.2207. Compound 3n: ¹H
NMR (400 MHz, CDCl3): δ = 6.68
(br, 1 H), 4.30 (q, J = 7.2
Hz, 2 H), 4.21 (q, J = 7.2 Hz,
2 H), 3.44-3.34 (m, 1 H), 2.00-1.60 (m, 6 H),
1.52-1.17 (m, 10 H) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 177.1, 155.6,
153.1, 63.7, 62.4, 62.2, 43.9, 29.3, 28.9, 28.8, 25.7, 25.6, 25.5,
25.3, 14.3, 14.1 ppm. Anal. Calcd for C13H22N2O5Na [M + Na]+:
309.1421; found: 309.1421. Compound 3o: ¹H
NMR (400 MHz, CDCl3): δ = 7.34 (br,
10 H), 6.76 (br, 1 H), 5.24 (s, 2 H), 5.17 (s, 2 H), 3.46-3.26
(m, 1 H), 2.00-1.14 (m, 10 H) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 176.8, 155.4,
153.0, 135.3, 134.7, 128.6, 128.5, 128.4, 128.1, 69.1, 68.0, 43.9,
29.3, 28.8, 25.7, 25.5, 25.3 ppm. Anal. Calcd for C23H26N2O5Na [M + Na]+:
433.1734; found: 433.1738.