Indium mediated Barbier reactions of 1,2-diones: A facile synthesis of α-hydroxy ketones

Article abstract of DOI:10.1016/S0040-4039(99)02237-6

Indium mediated allylation and cinnamylation of 1,2-diones with the corresponding bromides in the presence of sodium iodide produce α-carbonyl homoallylic alcohols in excellent yields. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4039(99)02237-6

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 41 (2000) 1091–1094
Indium mediated Barbier reactions of 1,2-diones: a facile
synthesis of α-hydroxy ketones
Vijay Nair ∗ and C. N. Jayan
Organic Chemistry Division, Regional Research Laboratory (CSIR), Trivandrum-695 019, India
Received 22 September 1999; revised 25 November 1999; accepted 29 November 1999
Abstract
Indium mediated allylation and cinnamylation of 1,2-diones with the corresponding bromides in the presence
of sodium iodide produce α-carbonyl homoallylic alcohols in excellent yields. © 2000 Elsevier Science Ltd. All
rights reserved.
Keywords: Barbier reactions; indium; diones.
Ever since the discovery of indium mediated Barbier reactions of aldehydes and ketones by Araki et
al.,1 there has been considerable interest in this area.2 A variety of functional groups such as anhydrides,3
acid chlorides,4 imides,5 activated alkenes,6 alkynes,7 cyclopropenes8 etc. has been subjected to indium
mediated C–C bond forming reactions. However, except for the reports involving azetidinones,9 there
has been no work on indium mediated reactions of 1,2-diones.
In the context of our general interest in the chemistry of 1,2-diones,10 an exploration of the indium
mediated allylation of such compounds was carried out and our preliminary results indicating the utility
of this process in the synthesis of α-hydroxy carbonyl compounds are reported here. It is worthy of
mention that α-hydroxy carbonyl compounds are useful intermediates in synthesis.11
Our studies were initiated with the reaction of allyl bromide with acenaphthenequinone in the presence
of indium and sodium iodide in DMF which furnished 95% of the corresponding α-hydroxy carbonyl
compound 3 (Scheme 1).
Scheme 1.
∗
Corresponding author. Fax: 91-471-491712; e-mail: gvn@csrrltrd.ren.nic.in (V. Nair)
0040-4039/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(99)02237-6
tetl 16165

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This procedure12 offers a more convenient alternative to the Lewis acid mediated allylation using allyl
tin compounds.13 In order to assess the generality of the process, the reaction was studied with a variety
of 1,2-dicarbonyl compounds and the results are summarised in Table 1.
Table 1
Allylation of diones
Subsequently, it was found that the acenaphthenequinone undergoes facile cinnamylation14 also under
similar conditions, as illustrated by Scheme 2.
Scheme 2.
This reaction also appears to be general (Table 2). In certain cases, cinnamylation affords regioisomeric
mixtures of products which are separable. It may be noted that cinnamylation leading to both α and
γ isomers in certain cases is in keeping with the characteristic behaviour of other substituted allyl
organometallics.15 However, in the case of indium mediated Barbier reactions, Araki16 has suggested that
the steric environment of the carbonyl group may be responsible for the formation of the α-cinnamylated
product.
In conclusion, we have observed that the indium mediated allylation and cinnamylation of 1,2-diones
in the presence of NaI provides a rapid and operationally simple method for the synthesis of α-hydroxy
carbonyl compounds which may prove to be the method of choice. Further work is in progress.

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Table 2
Cinnamylation of diones
Acknowledgements
The authors thank Dr. P. Shanmugham and Ms. Soumini Mathew for the NMR spectra. C.N.J. thanks
CSIR, Government of India, for the award of research fellowship.
References
1. Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem. 1988, 53, 1831–1833.
2. Cintas, P. Synlett 1995, 1087–1096.
3. Araki, S.; Katsumura, N.; Ito, H.; Butsugan, Y. Tetrahedron Lett. 1989, 30, 1581–1582.
4. Yadav, J.; Srinivas, D.; Reddy, G. S.; Bindu, K. H. Tetrahedron Lett. 1997, 38, 8745–8748.
5. Araki, S.; Shimizu, T.; Johar, P. S.; Jin, S.-J.; Butsugan, Y. J. Org. Chem. 1991, 56, 2538–2542.
6. Wang, L.; Sun, X.; Zhang, Y. Synth. Commun. 1998, 28, 3263–3267.
7. (a) Araki, S.; Imai, A.; Shimizu, K.; Butsugan, Y. Tetrahedron Lett. 1992, 33, 2581–2582. (b) Araki, S.; Imai, A.; Shimizu,
K.; Mori, A.; Yamada, M.; Butsugan, Y. J. Org. Chem. 1995, 60, 1841–1847. (c) Ranu, B. C.; Majee, A. Chem. Commun.
1997, 1225–1226. (d) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62, 2318–2319.
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1998, 39, 6327–6330.
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H.; Yoshikoshi, A. J. Org. Chem. 1986, 51, 1478–1481.
12. Typical experimental procedure: A mixture of the 1,2-dione (1 mmol), allyl bromide(1.55 mmol) indium powder (Aldrich
chemicals) (1.05 mmol) and sodium iodide (1.55 mmol) in dimethylformamide (3 mL) was stirred at 25°C until completion
of the reaction (TLC). The reaction mixture was quenched with a few drops of 1N HCl and extracted with diethylether.
Evaporation of the solvent followed by purification of the product by silica gel column chromatography provided the pure
product.

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13. Naruta, Y. J. Am. Chem. Soc. 1980, 102, 3774–3783.
14. Data of the product 9. IR (KBr): 3474, 1695, 1595, 1339, 1195, 970, 746 cm−1. 1H NMR (CDCl3) δ: 2.70(1H, m), 2.95(1H,
m), 3.4(1H, b, -OH), 6.13(1H, m), 6.37(1H, d), 7.13–7.18(5H, m), 7.61–8.08(6H, m); 13C NMR 42.03, 79.79, 120.98,
122.25, 122.69, 125.36, 126.29, 127.42, 128.32, 128.48, 128.74, 130.67, 132.03, 134.99, 137.05, 139.44, 141.32, 205.17;
CHN calcd: C(83.98), H(5.37). Observed: C(83.86), H(5.44).
15. Yamamoto,Y.; Asao, N. Chem. Rev. 1993, 93, 2207–2293.
16. Araki, S.; Katsumura, N.; Butsugan, Y. J. Organomet. Chem. 1991, 415, 7–24.