Synlett 2015; 26(16): 2237-2242
DOI: 10.1055/s-0035-1560071
letter
© Georg Thieme Verlag Stuttgart · New York

Dichotomous Reaction Pathways for the Oxidative Palladium(II)-Catalyzed Intramolecular Acyloxylation of Alkenes

Fadila Louafi
a  Sorbonne Universités, UPMC Univ Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, , FR2769 Institut de Chimie Moléculaire, F-75005 Paris, France   Email: julie.oble@upmc.fr   Email: giovanni.poli@upmc.fr
b  CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire, F-75005 Paris, France
,
Mélanie M. Lorion
a  Sorbonne Universités, UPMC Univ Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, , FR2769 Institut de Chimie Moléculaire, F-75005 Paris, France   Email: julie.oble@upmc.fr   Email: giovanni.poli@upmc.fr
b  CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire, F-75005 Paris, France
,
Julie Oble*
a  Sorbonne Universités, UPMC Univ Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, , FR2769 Institut de Chimie Moléculaire, F-75005 Paris, France   Email: julie.oble@upmc.fr   Email: giovanni.poli@upmc.fr
b  CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire, F-75005 Paris, France
,
Giovanni Poli*
a  Sorbonne Universités, UPMC Univ Paris 06, UMR 8232, Institut Parisien de Chimie Moléculaire, , FR2769 Institut de Chimie Moléculaire, F-75005 Paris, France   Email: julie.oble@upmc.fr   Email: giovanni.poli@upmc.fr
b  CNRS, UMR 8232, Institut Parisien de Chimie Moléculaire, F-75005 Paris, France
› Author Affiliations
Further Information

Publication History

Received: 11 May 2015

Accepted after revision: 09 July 2015

Publication Date:
07 September 2015 (eFirst)

Abstract

This work provides an in-depth investigation of the Pd(II)-catalyzed oxidative cyclization of various alkenoic acids bearing different tethers between the carboxylic acid moiety and the olefin function, showcasing how different mechanistic pathways (oxypalladation or allylic C–H activation) can be operative. The factors biasing toward one or the other of these reactivities are rationally discussed and compared with our recent studies on the Pd(II)-catalyzed intramolecular amination.

Supporting Information

 
  • References and Notes

  • 1 On leave from UR-CHEMS, Université Constantine 1, 25000 Constantine, Algeria.

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  • 29 Given the complexity of the crude 1H NMR spectrum, we were not able to determinate the diastereomeric ratios for compounds 5 and 6. Although we did not optimize this domino sequence, the results still confirm our conclusions concerning the involvement of the cyclic OxPI intermediate.
    • 30a General Procedures; Conditions A: In a sealed tube, under an argon atmosphere, were added the carboxylic acid (1.0 equiv), Pd(OAc)2 (0.1 equiv), bis-sulfoxide ligand (0.15 equiv), p-phenylbenzoquinone (1.07 equiv), NaOAc (1.0 equiv) and CH2Cl2 (0.5 M). The tube was sealed and the reaction was allowed to stir at 45 °C. After 24 h, the reaction mixture was filtered on a plug of celite. The filtrate was treated with a sat. aq solution of 5% K2CO3 and the aqueous layer was extracted with CH2Cl2 (3 ×). The combined organic layers were dried over anhyd MgSO4, filtered and concentrated under reduced pressure. Purification by flash silica gel column chromatography afforded the desired vinyl lactone. Analytical Data for 2b: Yield: 59%; colorless oil. 1H NMR (300 MHz, CDCl3): δ = 5.86 (ddd, J = 17.1, 10.5, 6.0 Hz, 1 H), 5.33 (dt, J = 17.2, 1.2 Hz, 1 H), 5.22 (dt, J = 10.5, 1.1 Hz, 1 H), 4.87–4.95 (m, 1 H), 2.50 (ddd, J = 8.0, 6.9, 1.1 Hz, 2 H), 2.31–2.46 (m, 1 H), 1.87–2.07 (m, 1 H). These data are in good agreement with those reported in the literature (ref. 11). Conditions B: In a sealed tube, under an argon atmosphere, were added the carboxylic acid (1.0 equiv), Pd(OAc)2 (0.1 equiv), bis-sulfoxide ligand (0.15 equiv), iodobenzene diacetate (2.1 equiv), NaOAc (1.0 equiv) and CH2Cl2 (0.5 M). The tube was sealed and the reaction was allowed to stir at 45 °C for 24 h. The mixture was filtered over a small pad of celite. The filtrate was treated with a sat. aq solution of 5% K2CO3 and the aqueous layer was extracted with CH2Cl2 (3 ×). The combined organic layers were dried over anhyd MgSO4, filtered and concentrated under reduced pressure. Purification by flash silica gel column chromatography afforded the acetoxylated product. Analytical Data for 3b: yield: 41%; yellow oil. 1H NMR (300 MHz, CDCl3): δ = 4.45–4.53 (m, 1 H), 4.18 (dd, J = 12.0, 3.8 Hz, 1 H), 4.12 (dd, J = 12.0, 5.8 Hz, 1 H), 2.30–2.74 (m, 2 H), 2.04 (s, 3 H), 1.70–2.00 (m, 3 H), 1.50–1.71 (m, 1 H).
    • 30b These data are in good agreement with those reported in the literature: Ha HJ, Park YS, Park GS. ARKIVOC 2001; (i): 55