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DOI: 10.1055/s-0029-1218374
A Chiral Bifunctional Sulfonamide as an Organocatalyst: Alcoholysis of σ-Symmetric Cyclic Dicarboxylic Anhydrides
Publikationsverlauf
Publikationsdatum:
18. November 2009 (online)

Abstract
Enantioselective alcoholysis of σ-symmetric cyclic dicarboxylic anhydrides with benzyl alcohol catalyzed by a chiral bifunctional sulfonamide was achieved in up to 98% ee at 5 mol% loading.
Key words
anhydrides - asymmetric synthesis - homogeneous catalysis - sulfonamides - alcoholysis
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
General Experimental
Procedure for Chiral Sulfonamide 1 Catalyzed Alcoholysis of Cyclic Dicarboxylic
Anhydrides
To a solution of 3-phenylglutaric anhydride
(2a, 190 mg, 1.0 mmol) and chiral sulfonamide 1 (25.8 mg, 0.05 mmol) in Et2O
(10 mL) was added BnOH (125 µL, 1.2 mmol) at r.t. After
stirring at r.t. for 20 h, the reaction mixture was treated with
10% HCl followed by extraction with CHCl3. The extract
was dried over anhyd MgSO4, filtered, and concentrated
in vacuo. To a solution of the residue in benzene-MeOH
(7:2, 9 mL) was added a solution of TMSCHN2 (2.0 M in
Et2O, 1 mL, 2.0 mmol). After being stirred at r.t. for
15 min, the reaction mixture was evaporated in vacuo. The oily residue
was purified by silica gel column chromatography [EtOAc-n-hexane (1:4)] to afford methyl ester
(S)-4a (286
mg, 92% yield, 87% ee) as a colorless oil. The
ee (%) of (S)-4a was
determined on a Chiralpak AD-H column [Daicel, eluent: n-hexane-2-PrOH (15:1), flow
rate: 1 mL/min, detection: 254 nm]. The retention
times were 12.5 min [minor isomer, (R)-4a] and 13.8 min [major
isomer, (S)-4a],
respectively. The absolute configuration of (S)-4a was explicitly determined by its chemical
conversion to thioester (S)-5 (Scheme
[¹]
).
[7]

Scheme1
For details see Supporting Information.