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Synlett 2012(3): 393-396  
DOI: 10.1055/s-0031-1290311
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Rh(I)-Catalyzed Cyclocarbonylation of Enynes with Glyceraldehyde: An Available Carbonyl Source Derived from Sugar Alcohols

Keiichi Ikeda, Tsumoru Morimoto*, Takayuki Tsumagari, Hiroki Tanimoto, Yasuhiro Nishiyama, Kiyomi Kakiuchi
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), Takayama, Ikoma, Nara 630-0192, Japan
Fax: +81(743)726081; e-Mail: morimoto@ms.naist.jp;
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Publication History

Received 20 October 2011
Publication Date:
19 January 2012 (online)

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Abstract

Catalytic cyclocarbonylation reactions using a glyceraldehyde derivative as a carbonyl source are described. The rhodium(I)-catalyzed reaction of enynes with glyceraldehyde acetonide gave bicyclic cyclopentenones as the products. This presents an interesting use of a sugar alcohol derived carbon resource as well as a convenient procedure for the cyclocarbonylation of enynes.

Key words

rhodium - cyclocarbonylation - enyne - glyceraldehyde - sugar alcohol

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Under identical reaction conditions, the use of glycerol itself as a carbonyl source gave 3a only in 11% yield, along with 13% of the hydrogen adduct of 2a and 30% of a mixture of dimers of 2a.

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Typical Procedure for the Rhodium-Catalyzed Cyclocarbonylation Reaction of Enyne 2a with Glyceraldehyde Acetonide ( R )-1 (Conditions A) To a suspension of [RhCl(cod)]2 (6.16 mg, 0.0125 mmol), dppp (10.63 mg, 0.025 mmol), and (R)-1 (131.0 mg, 1.0 mmol) in anhyd toluene (1 mL) was added enyne 2a (86.1 mg, 0.5 mmol) under N2. After degassing the mixture through three freeze-pump-thaw cycles, the solution was stirred at reflux for an appropriate time. The reaction mixture was evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with hexane-EtOAc (v/v = 2:1) as the eluent.
Compound 3a
Yield: 87%; colorless oil; R f = 0.31 (hexane-EtOAc, 2:1). ¹H NMR (500 MHz, CDCl3): δ = 2.31 (dd, J = 17.5, 2.4 Hz, 1 H), 2.82 (dd, J = 17.5, 6.4 Hz, 1 H), 3.27-3.32 (m, 1 H), 3.19-3.23 (m, 1 H), 4.35 (t, J = 7.6 Hz, 1 H), 4.56 (d, J = 16.2 Hz, 1 H), 4.91 (d, J = 16.2 Hz, 1 H), 7.33-7.38 (m, 3 H), 7.49 (d, J = 6.7 Hz, 2 H). ¹³C NMR (125 MHz, CDCl3): δ = 40.3, 43.2, 66.2, 71.3, 128.0, 128.5, 128.6, 130.5, 134.6, 177.4, 206.8.²a

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Using a combination of [IrCl(cod)]2 and (S)-tolBINAP, the reaction of 2a with (R)-1 in 1,4-dioxane at 120 ˚C resulted in the more enantioselective formation of (S)-3a (89% ee), although the chemical yield was much lower (31%).