Preparation of 1,3-diketones by the reaction of bis(iodozincio)methene with acyl cyanides or palladium-catalyzed reaction with acyl chlorides

Synlett

Volumn , Issue 3, 1998, Pages 267-268

  Matsubara, Seijiro ^a   Kawamoto, Kazunari ^a   Utimoto, Kiitiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0008463078     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1998-1647     Document Type: Article

References (10)

1. Marek, I.; Normant, J. F. Chem. Rev. 1996, 96, 3241.
2. Utimoto, K.; Toda, N.; Mizuno. T.; Kobara, M.; Matsubara, S. Angew, Chem. 1997, 109, 2886.
3. Takai, K.; Kakiuchi, T.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1994, 59, 2668.
4. Eisch, J. J.; Piotuwski, A. Tetrahedron Lett. 1983, 24, 2043.
5. Knochel, P.; Normant, J. F. Tetrahedron Lett. 1986, 27, 4427.
6. 2, in place of Wako zinc.
7. Reaction of bis(iodozincio)methane (1) with acyl cyanide 2: To a THF solution of 1 (3.6 mL of 0.55 M solution containing 2.0 mmol of 1), a THF (7.0 mL) solution of benzoyl cyanide (2, R = Ph; 262 mg, 2.0 mmol) was added at room temperature. After being stirred for 2 h at room temperature, the reaction mixture was added with 20 mL of 1 M aq. HCl. The mixture was extracted twice with ethyl acetate, then combined organic layer was washed, dried, concentrated, and purified by column chromatography. Dibenzoylmethane (3, R = Ph) was obtained in 90% yield.
8. Reaction of 1 with α,β-unsaturated acyl cyanide (2; R = PhCH=CH) proceeded both acylation and Michael addition (entry 8 in Table 1). Michael addition (or conjugated addition) of 1 to α,β-unsaturated carbonyl compounds will be published in a separate paper.
9. 3 (0.4 mmol), a THF solution of 1 (3.6 mL of 0.55 M solution containing 2.0 mmol of 1) was added. A THF solution (6 mL) of 6 (R = Ph, 263 mg, 2.0 mmol) was added dropwise to the reaction mixture maintained at -15 °C. After being stirred for 2 h, the reaction mixture was worked up as described above.
10. 4Cl powder. Product 10 was purified by distillation and chromatography.