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Synlett 2009(9): 1441-1444  
DOI: 10.1055/s-0029-1216747
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective γ-Lactam Synthesis via Palladium-Catalyzed Intramolecular Asymmetric Allylic Alkylation

Xavier Bantreila, Guillaume Prestat*a, David Madeca, Peter Fristrupb, Giovanni Poli*a
a Institut Parisien de Chimie Moléculaire (IPCM) - UMR 7201, UPMC Univ Paris 06, Case 183, 75005 Paris, France
Fax: +33(1)44277567; e-Mail: guillaume.prestat@upmc.fr; e-Mail: giovanni.poli@upmc.fr;
b Materials and Process Simulation Center (139-74), California Institute of Technology, Pasadena, CA 91125, USA
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Publication History

Received 13 February 2009
Publication Date:
04 May 2009 (online)

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Abstract

A Pd(0)-catalyzed intramolecular allylic alkylation in the presence of (R)-3,5-t-Bu-MeOBIPHEP takes place in up to 92:8 er in agreement with DFT calculations and provides easy access to enantioenriched disubstituted γ-lactams.

Key words

palladium - allylic alkylation - enantioselectivity

    References and Notes

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13

To a solution of allylpalladium chloride dimer (1.4 mg, 3.9 µmol, 2.5 mol%) in CH2Cl2 (500 µL) was added the bidentate ligand (11.7 µmol, 7.5 mol%). The solution was stirred at r.t. for 5 min. Then, a solution of acyclic substrate (0.157 mmol, 1 equiv) in 1.5 mL of CH2Cl2, BSA (46 µL, 0.188 mmol, 1.2 equiv), and KOAc (1.6 mg, 15.7 µmol, 0.1 equiv) were successively added. The resulting solution was stirred at the appropriate temperature until full conversion was reached. A sat. aq NH4Cl soln was added, and the aqueous phase was extracted three times with CH2Cl2. The collected organic phases were washed with brine, dried over MgSO4, and the solvent was removed in vacuo. The crude product was purified by flash chromatography.

24

To a solution of tetrabutyl ammonium bromide (0.1 equiv) in CH2Cl2 (500 µL) were added allylpalladium chloride dimer (1.4 mg, 3.9 µmol, 2.5 mol%), and the bidentate ligand (11.7 µmol, 7.5 mol%). The soln was stirred at r.t. for 5 min. Then, a soln of acyclic substrate (0.157 mmol, 1 equiv) in CH2Cl2 (1.5 mL), H2O (2 mL), and 50% KOH aq soln (63 µL, 0.314 mmol, 2 equiv) were successively added. The resulting biphasic system was stirred vigorously at r.t. for 2 h. A sat. aq NH4Cl soln was added, and the aqueous phase was extracted three times with CH2Cl2. The collected organic phases were washed with brine, dried over MgSO4, and the solvent was removed in vacuo. The crude product was purified by flash chromatography.

25

The instability of this ligand under the basic biphasic conditions might account for this result.

29

Jaguar, version 7.5, release 207, Schrödinger, LLC, New York, NY, 2008.

30

Fristrup P., Norrby P. O., unpublished results.