Asymmetric Baeyer-Villiger Oxidation of Prochiral Cyclobutanones Using a Chiral Cationic Palladium(II) 2-(Phosphinophenyl)pyridine Complex as Catalyst

Katsuji Ito; Ayako Ishii; Tomomi Kuroda; Tsutomu Katsuki

doi:10.1055/s-2003-38377

LETTER

Asymmetric Baeyer-Villiger Oxidation of Prochiral Cyclobutanones Using a Chiral Cationic Palladium(II) 2-(Phosphinophenyl)pyridine Complex as Catalyst

Katsuji Ito*^a, Ayako Ishii^a, Tomomi Kuroda^a, Tsutomu Katsuki*^b
^a Department of Chemistry, Fukuoka University of Education, CREST, Japan Science and Technology (JST), Akama, Munakata, Fukuoka, 811-4192, Japan
Fax: +81(940)351367; e-Mail: itokat@fukuoka-edu.ac.jp;
^b Department of Chemistry, Faculty of Science, Graduate School, Kyushu University 33, CREST, Japan Science and Technology (JST), Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

Abstract

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Abstract

Chiral cationic palladium(II) 2-(phosphinophenyl)pyridine (1a) complex was found to be an effective catalyst for asymmetric Baeyer-Villiger oxidation of prochiral cyclobutanones. For example, good and excellent enantioselectivities (80% and >99% ees) were achieved in the reactions of 3-phenylcyclobutanone and a tricyclic cyclobutanone, respectively.

Key words

asymmetric Baeyer-Villiger oxidation - asymmetric catalysis - palladium - chiral P-N ligand

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References

<A NAME="RU01803ST-1">1</A> Bolm C. Beckmann O. Luong TKK. In Transition Metals for Organic Synthesis Vol. 2: Beller M. Bolm C. Wiley-VCH; Weinheim: 1998. p.213

<A NAME="RU01803ST-2">2</A> (a) Bolm C. Schlingloff G. Weickhardt K. Angew. Chem., Int. Ed. Engl. 1994, 33: 1848

<A NAME="RU01803ST-2">2</A> (b) Gusso A. Baccin C. Pinna F. Strukul G. Organometallics 1994, 13: 3442

<A NAME="RU01803ST-3">3</A> (a) Bolm C. Beckmann O. In Comprehensive Asymmetric Catalysis Vol. 2: Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. p.803

<A NAME="RU01803ST-3">3</A> (b) Strukul G. Angew. Chem. Int. Ed. 1998, 37: 1198

<A NAME="RU01803ST-4A">4a</A> Bolm C. Schlingloff G. J. Chem. Soc., Chem. Commun. 1995, 1247

<A NAME="RU01803ST-4B">4b</A> Bolm C. Schlingloff G. Bienewald F. J. Mol. Cat. A: Chem. 1997, 117: 347

<A NAME="RU01803ST-4C">4c</A> Strukul G. Varagnolo A. Pinna F. J. Mol. Cat. A: Chem. 1997, 117: 413

<A NAME="RU01803ST-4D">4d</A> Bolm C. Luong KK. Schlingloff G. Synlett 1997, 1151

<A NAME="RU01803ST-4E">4e</A> Paneghetti C. Gavagnin R. Pinna F. Strukul G. Organometallics 1999, 18: 5057

<A NAME="RU01803ST-4F">4f</A> Bolm C. Beckmann O. Cosp A. Palazzi C. Synlett 2001, 1461

<A NAME="RU01803ST-4G">4g</A> Peng Y. Feng X. Yu K. Li Z. Jiang Y. Yeung C.-H. J. Orgmet. Chem. 2001, 619: 204

<A NAME="RU01803ST-4H">4h</A> Bolm C. Beckmann O. Palazzi C. Can. J. Chem. 2001, 79: 1593

<A NAME="RU01803ST-4I">4i</A> Miyatake Y. Nishibayashi Y. Uemura S. Bull. Chem. Soc. Jpn. 2002, 75: 2233

<A NAME="RU01803ST-4J">4j</A> Murahashi S.-I. Ono S. Imada Y. Angew. Chem. Int. Ed. 2002, 41: 2366

For stoichiometric B-V reactions, see:

<A NAME="RU01803ST-5A">5a</A> Lopp M. Paju A. Kanger T. Pehk T. Tetrahedron Lett. 1996, 37: 7583

<A NAME="RU01803ST-5B">5b</A> Kanger T. Kriis K. Paju A. Pehk T. Lopp M. Tetrahedron: Asymmetry 1998, 9: 4475

<A NAME="RU01803ST-5C">5c</A> Bolm C. Beckmann O. Chirality 2000, 12: 523

<A NAME="RU01803ST-5D">5d</A> Shinohara T. Fujioka S. Kotsuki H. Heterocycles 2001, 55: 237

<A NAME="RU01803ST-5E">5e</A> Aoki M. Seebach D. Helv. Chim. Acta 2001, 84: 187

<A NAME="RU01803ST-6A">6a</A> Alphand V. Furstoss R. In Handbook of Enzyme Catalysis in Organic Synthesis Vol. 2: Drauz K. Waldmann H. VCH Publishers; Weinheim: 1995. p.744

<A NAME="RU01803ST-6B">6b</A> Stewart JD. Curr. Org. Chem. 1997, 2: 211

<A NAME="RU01803ST-6C">6c</A> Kayser M. Chen G. Stewart J. Synlett 1999, 153

<A NAME="RU01803ST-6D">6d</A> Kelly DR. Chemica Oggi/Chemical Today 2000, 18

<A NAME="RU01803ST-6E">6e</A> Kelly DR. Chemica Oggi/Chemical Today 2000, 33

<A NAME="RU01803ST-6F">6f</A> Kelly DR. Chemica Oggi/Chemical Today 2000, 52

<A NAME="RU01803ST-6G">6g</A> Alphand V. Furstoss R. In Asymmetric Oxidation Reactions: A Practical Approach Katsuki T. Oxford University Press; Oxford: 2001. p.214

<A NAME="RU01803ST-6H">6h</A> Mihovilovic MD. Muller B. Stanetty P. Eur. J. Org. Chem. 2002, 3711

<A NAME="RU01803ST-7A">7a</A> Uchida T. Katsuki T. Tetrahedron Lett. 2001, 42: 6911

<A NAME="RU01803ST-7B">7b</A> Watanabe A. Uchida T. Ito K. Katsuki T. Tetrahedron Lett. 2002, 43: 4481

<A NAME="RU01803ST-7C">7c</A> Uchida T. Katsuki T. Ito K. Akashi S. Ishii A. Kuroda T. Helv. Chim. Acta. 2002, 85: 3078

The geometrical problem is avoided, when a C ₂-symmetric ligand is used.

<A NAME="RU01803ST-9A">9a</A> Ito K. Katsuki T. Tetrahedron Lett. 1993, 34: 2661

<A NAME="RU01803ST-9B">9b</A> Ito K. Katsuki T. Chem. Lett. 1994, 1857

<A NAME="RU01803ST-9C">9c</A> Ito K. Yoshitake M. Katsuki T. Tetrahedron 1996, 52: 3905

<A NAME="RU01803ST-9D">9d</A> Ito K. Yoshitake M. Katsuki T. Heterocycles 1996, 42: 305

<A NAME="RU01803ST-9E">9e</A> Ito K. Kashiwagi R. Iwasaki K. Katsuki T. Synlett 1999, 1563

<A NAME="RU01803ST-9F">9f</A> Ito K. Kashiwagi R. Hayashi S. Uchida T. Katsuki T. Synlett 2001, 284

<A NAME="RU01803ST-10A">10a</A> von Matt P. Pfaltz A. Angew. Chem. Int. Ed. Engl. 1993, 32: 566

<A NAME="RU01803ST-10B">10b</A> Sprinz J. Helmchen G. Tetrahedron Lett. 1993, 34: 1769

<A NAME="RU01803ST-10C">10c</A> Dawson GJ. Frost CG. Williams JMJ. Coote SJ. Tetrahedron Lett. 1993, 34: 3149

<A NAME="RU01803ST-10D">10d</A> Loiseleur O. Meier P. Pfaltz A. Angew. Chem., Int. Ed. Engl. 1996, 35: 200

Typical experimental procedure To a solution of bis(benzonitrile)palladium(II) chloride (1.9 mg, 5.0 mol) in THF (0.4 mL) was added ligand 1a (2.3 mg, 5.5 mol) under nitrogen and stirred at room temperature for 1 h. Silver hexafluoroantimonate (3.4 mg, 10 mol) was placed another flask under nitrogen and to this flask was added the above palladium(II)-1a dichloride solution. After being stirred for 1 h at room temperature, the mixture was filtered through a pad of Celite under nitrogen. To the filtrate was added 3-phenylcyclobutanone (15.2 mg, 0.1 mmol) and then cooled to -60 °C. To the cooled solution was added UHP (12.2 mg, 0.13 mmol) and the mixture was further stirred at the temperature for 214 h. The mixture was concentrated and the residue was chromatographed on silica gel (hexane-EtOAc, 9:1) to give dihydro-4-phenylfuran-2(3H)-one (14.8 mg, 91%). The enantiomeric excess of the product was determined to be 80% ee by HPLC analysis using chiral stationary phase column (Daicel Chiralpak AD-H; hexane-i-PrOH, 95:5).