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DOI: 10.1055/s-0031-1290311
Rh(I)-Catalyzed Cyclocarbonylation of Enynes with Glyceraldehyde: An Available Carbonyl Source Derived from Sugar Alcohols
Publikationsverlauf
Publikationsdatum:
19. Januar 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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References and Notes
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.
11
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
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%).