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: [email protected]; e-Mail: [email protected];
b Materials and Process Simulation Center (139-74), California Institute of Technology, Pasadena, CA 91125, USA
Further Information

Publication History

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

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.

    References and Notes

  • 1 Giambastiani G. Pacini B. Porcelloni M. Poli G. J. Org. Chem.  1998,  63:  804 
  • 2a Poli G. Giambastiani G. J. Org. Chem.  2002,  67:  9456 
  • 2b Lemaire S. Giambastiani G. Prestat G. Poli G. Eur. J. Org. Chem.  2004,  2840 
  • 2c Bui The Thuong M. Sottocornola S. Prestat G. Broggini G. Madec D. Poli G. Synlett  2007,  1521 
  • 2d See also: Craig D. Hyland CJT. Ward SE. Synlett  2006,  2142 
  • 3 Trost BM. Strege PE. J. Am. Chem. Soc.  1977,  99:  1649 
  • 4a Trost BM. Van Vranken DL. Chem. Rev.  1996,  96:  395 
  • 4b Pfaltz A. Lautens M. Allylic Substitution Reactions, In Comprehensive Asymmetric Catalysis II   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin / Heidelberg / New York: 1999.  p.834-884  
  • 4c Trost BM. Crawley ML. Chem. Rev.  2003,  103:  2921 
  • 4d Trost BM. J. Org. Chem.  2004,  69:  5813 
  • 4e Lu Z. Ma S. Angew. Chem. Int. Ed.  2007,  47:  258 
  • 5 Yamamoto K. Tsuji J. Tetrahedron Lett.  1982,  23:  3089 
  • 6a Genêt J.-P. Grisoni S. Tetrahedron Lett.  1988,  29:  4543 
  • 6b Kardos N. Genêt J.-P. Tetrahedron: Asymmetry  1994,  5:  1525 
  • 7 Koch G. Pfaltz A. Tetrahedron: Asymmetry  1996,  7:  2213 
  • 8 Trost BM. Sacchi KL. Schroeder GM. Asakawa N. Org. Lett.  2002,  4:  3427 
  • 9 Bian J. Van Wingerden M. Ready JM. J. Am. Chem. Soc.  2006,  128:  7428 
  • 10a

    We assume a reversible pre-equilibrium for the initial complexation between Pd(0)L complex and the double bond of the substrate.

  • 10b Although the enantiodiscriminating step of an AAA is expected to be also the rate-determining one, such a correspondence is not always met in enantioselective transformations. See, for example: Kramer R. Brückner R. Chem. Eur. J.  2007,  13:  9076 
  • 11 Fristrup P. Jensen T. Hoppe J. Norrby P.-O. Chem. Eur. J.  2006,  12:  5352 
  • 12 Norrby P.-O. Mader MM. Vitale M. Prestat G. Poli G. Organometallics  2003,  22:  1849 
  • 14 Miyashita A. Yasuda A. Takaya H. Toriumi K. Ito T. Souchi T. Noyori R. J. Am. Chem. Soc.  1980,  102:  7932 
  • 15 The er has been preferred to ee as enantioselectivity descriptor. See: Gawley RE. J. Org. Chem.  2006,  71:  2411 
  • 16 The absolute configuration of 2 was determined by conver-sion of an enantioenriched sample of it (er 86:14) into N-benzoyl-3-ethylpyrrolidine and comparison of its optical rotation with that reported for the enantiopure R-config-urated sample described by Pedrosa et al.: Andres C. Duque-Soladana JP. Pedrosa R. J. Org. Chem.  1999,  64:  4273 
  • 17 Schmid R. Foricher J. Cereghetti M. Schônholzer P. Helv. Chim. Acta  1991,  74:  370 
  • 18a Jeulin S. Duprat de Paule S. Ratovelomanana-Vidal V. Genêt J.-P. Champion N. Angew. Chem. Int. Ed.  2004,  43:  320 
  • 18b Jeulin S. Duprat de Paule S. Ratovelomanana-Vidal V. Genêt J.-P. Champion N. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5799 
  • 19a Duprat de Paule S, Champion N, Ratovelomanana-Vidal V, Genêt J.-P, and Dellis P. inventors; FR  2830254.  2001
  • 19b Duprat de Paule S, Champion N, Ratovelomanana-Vidal V, and Genêt J.-P. inventors; Dellis P. WO  03029259.  2003
  • 19c Duprat de Paule S. Jeulin S. Ratovelomanana-Vidal V. Genêt J.-P. Champion N. Dellis P. Tetrahedron Lett.  2003,  44:  823 
  • 20 Schmid R. Broger EA. Cereghetti M. Crameri Y. Foricher J. Lalonde M. Müller RK. Scalone M. Schoettel G. Zutter U. Pure Appl. Chem.  1996,  68:  131 
  • 21 Trabesinger G. Albinati A. Feiken N. Kunz RW. Pregosin PS. Tschoerner M. J. Am. Chem. Soc.  1997,  119:  6315 
  • 22 Madec D. Prestat G. Martini E. Fristrup P. Poli G. Norrby P.-O. Org. Lett.  2005,  7:  995 
  • 23a Maitro G. Prestat G. Madec D. Poli G. Synlett  2006,  1055 
  • 23b Maitro G. Prestat G. Madec D. Poli G. J. Org. Chem.  2006,  71:  7449 
  • 26a Lee C. Yang W. Parr RG. Phys. Rev. B  1988,  37:  785 
  • 26b Becke AD. J. Chem. Phys.  1993,  98:  5648 
  • 26c Stephens PJ. Devlin FJ. Chabalowski CF. Frisch MJ. J. Phys. Chem.  1994,  98:  11623 
  • 27 LACVP* uses the 6-31G* basis set for all light elements, and the Hay-Wadt ECP and basis set for Pd: Hay PJ. Wadt WR. J. Chem. Phys.  1985,  82:  299 
  • THF: dielectric constant: 9.08, probe radius: 2.33237.
  • 28a Marten B. Kim K. Cortis C. Friesner RA. Murphy RB. Ringnalda MN. Sitkoff D. Honig B. J. Phys. Chem.  1996,  100:  11775 
  • 28b Tannor DJ. Marten B. Murphy R. Friesner RA. Sitkoff D. Nicholls A. Ringnalda M. Goddard WA. Honig B. J. Am. Chem. Soc.  1994,  116:  11875 
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.