References and Notes
For recent reviews of the Pauson-Khand
reaction, see:
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For reviews on the synthetic transformation
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Pagliaro M.
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<A NAME="RU57611ST-7">7</A> For a review on the synthetic transformation
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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.
<A NAME="RU57611ST-11">11</A>
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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<A NAME="RU57611ST-13">13</A>
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%).
